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Abstract
spc-Ni/MgAl (spc: solid-phase crystallization method) catalysts have been prepared from Mg–Al hydrotalcite-like compounds con-
taining Ni at the Mg site as the precursors and tested for partial oxidation of CH4 into synthesis gas. The precursors based on
[Mg2+ 3+ x+ − 2+ ions were replaced by Ni2+ ions, were
1−x Alx (OH)2 ] (CO3 x ) mH2 O, in which a ratio of Mg/Al varied and a part of the Mg
prepared by a coprecipitation method, thermally decomposed, and reduced to form spc-Ni/MgAl catalyst. Surface areas of spc-Ni/MgAl
catalysts were around 150 m2 g−1cat . Ni
2+ ions first substituted a part of the Mg2+ sites in the Mg–Al hydrotalcite-like compounds and then
incorporated in the rock-salt-type Mg–Ni–O solid solutions in the mixed oxide after the decomposition. The dispersion of Ni was thus re-
peatedly enhanced during the spc preparation, resulting in the highly dispersed Ni metal particles after the reduction. The activity of the
spc-Ni/MgAl catalyst was the highest at the ratio of Mg/Al of 1/3. When the catalysts were tested in the partial oxidation of CH4 , spc-
Ni0.5 /Mg2.5 Al afforded enough high CH4 conversion even at the high space velocity (9 × 105 ml h−1 g−1 cat ), exceeding the value obtained
over 1 wt% Rh/MgO. Ni species on spc-Ni0.5 /Mg2.5 Al catalysts were stable even under the presence of O2 , while Ni catalysts prepared
by the conventional impregnation quickly lost activity due to the surface oxidation of Ni particles. Moreover, the total heat produced by the
reaction was the lowest over the spc-Ni0.5 /Mg2.5 Al catalyst among the catalysts tested. This strongly suggests that the heat of exothermic
CH4 combustion to H2 O and CO2 could be quickly consumed by the following endothermic CH4 reforming by H2 O and CO2 over spc-
Ni0.5 /Mg2.5 Al. Thus, the spc-Ni0.5 /Mg2.5 Al catalyst is a hopeful candidate for the autothermal reforming of CH4 which can be carried out
under the copresence of both H2 O and O2 to feed H2 to the fuel cell economically. Actually the autothermal reforming of CH4 has been
successfully carried out over spc-Ni0.5 /Mg2.5 Al catalysts.
2003 Elsevier Inc. All rights reserved.
Keywords: Autothermal reforming of CH4 ; Solid-phase crystallization method; Supported Ni catalysts; Mg–Al hydrotalcite; High dispersion; Stable Ni metal
particles
and air contamination in the fuel gas could not be avoided. 2. Experimental
Recently supported precious metal catalysts have frequently
been reported to solve these problems [4–11], since the pre- 2.1. Preparation of the catalyst
cious metals such as Rh and Ru are highly active and stable
for the reforming reactions. However, the cost of the fabri- spc-Ni/MgAl catalysts with various Mg/Al ratios were
cation of the fuel cell system is also important, since a large prepared by the spc method as follows: Mg–Al hydrotal-
cite precursors based on [Mg2+ −
1−x Alx (OH)2 ] (CO3 x ) ·
3+ x+
amount of precious metals is required not only for the re-
2+
mH2 O, in which a part of Mg was replaced by Ni , were 2+
former but also for the fuel cell. Use of cheaper metals or, at
least, a smaller amount of precious metals is preferable for prepared by the coprecipitation method reported by Miyata
the catalyst preparation of the reformer. These restrictions et al. [27] with minor modifications. The loading amount
inevitably require a new concept for the catalyst preparation of Ni was fixed at 16.3 wt% after heating at 1073 K. Both
and also for its use in the reformer. an aqueous solution containing the nitrates of Mg2+ , Ni2+ ,
Supported metal catalysts have been used in the re- and Al3+ and an aqueous solution of sodium hydroxide were
forming reactions of hydrocarbons and are conventionally added slowly and simultaneously with vigorous stirring into
prepared by wet impregnation of different supports. This an aqueous solution of sodium carbonate. During the mix-
method is not fully reproducible and may give rise to some ing treatment, heavy slurry precipitated. The crystal growth
inhomogeneity in the distribution of the metal on the sur- took place by aging the solution at 333 K for 12 h. After
face. Moreover, the fine metal particles tend to sinter at high the solution was cooled to room temperature, the precipitate
temperature, resulting in the catalyst deactivation. Use of was washed with distilled water and dried in air at 353 K.
the precursors containing metal ions in the crystal struc- The Mg(Ni)–Al hydrotalcite-like precursors, thus obtained,
ture, which on further calcination and reduction, may result were heated in a muffle furnace in a static air atmosphere
in the formation of highly dispersed and stable metal parti- by increasing the temperature from ambient temperature to
cles on the surface. The authors have applied this method 1123 K at a rate of 5 K min−1 and kept at 1123 K for 5 h to
for the preparation of stable and highly dispersed metal- form the precursor of spc-Ni/MgAl. Surface areas of the pre-
supported catalysts as the “solid-phase crystallization” (spc) cursors of spc-Ni/MgAl catalysts were always high around
method and tested it by using perovskite as the precursors 150 m2 g−1cat . The catalysts were pressed at 25 tons, crushed,
[12–15]. and sieved to particles of prescribed size, which were used
in the reaction after the prereduction treatment.
The hydrotalcite-like compound is anionic clay, layered
As the reference, the catalysts were prepared by conven-
mixed hydroxides containing exchangeable anions and pro-
tional impregnation (imp) using α-Al2 O3 , γ -Al2 O3 , MgO,
duces the oxide by heating that shows interesting proper-
and Mg–Al mixed oxides prepared from Mg/Al (3/1) hy-
ties, such as high surface area, “memory effect,” and ba-
drotalcite as the carrier. When the Mg–Al mixed oxide was
sic character [16]. Moreover, upon heating, the compound
used as the carrier, water or acetone was used as the solvent
forms a homogeneous mixture of oxides with very small
of Ni(NO3 )2 · 2H2 O and the catalyst obtained was denoted as
crystal size, stable against thermal treatments, which by
imp-Ni/Mg3Al-aq or imp-Ni/Mg3Al-ac. Ni(acac)2 was also
reduction form small and thermally stable metal crystal-
used in acetone solution for impregnation and the catalyst
lites. Preparation of heterogeneous catalysts from Mg–Al was denoted as imp-Ni/Mg3Al-acac. The loading amount of
hydrotalcite-like compounds as the precursors and its uti- Ni was fixed at 16.3 wt% on all the catalysts after the heat-
lization for the CH4 reforming have been claimed [17] and ing.
reported by Basini et al. [18,19]. They focused their study
on the catalyst application in the CH4 partial oxidation, 2.2. Characterization of the catalyst
and the effects of the residence time and the thermal pro-
file were monitored to know the catalytic reaction mecha- The structures of the catalysts were studied by XRD,
nism. BET, TEM, TPR, and a H2 -adsorption method. X-ray dif-
We have recently reported that spc-Ni/MgAl catalysts fraction was measured by using a Rigaku RINT 2550VHF
were prepared starting from Mg–Al hydrotalcite-like com- diffractometer with Cu-Kα radiation. The diffraction pat-
pounds containing Ni at the Mg sites as the precursors, and terns were identified by a comparison with those included
were successfully applied for partial oxidation [20], steam in the JCPDS data base (Joint Committee of Powder Dif-
reforming [21], and dry reforming of CH4 [22–25]. It was fraction Standards). BET measurements were conducted us-
concluded that the high catalytic performance is uniquely ing N2 at 77 K with a Bell Japan BELSORP18 instru-
due to the stable and highly dispersed Ni metal particles on ment. Transmission electron micrographs (TEM) were ob-
the catalysts [26]. In the present paper, we report the effects tained over on a JEOL JEM3000F instrument equipped
of Mg/Al ratio and reduction temperature on the Ni disper- with a Hitachi/Kevex H-8100/DeltaIV EDS. Temperature-
sion on a spc-Ni/MgAl catalyst, and finally its high activity programmed reduction (TPR) of the catalyst was performed
revealed even at high space velocity in the autothermal re- with a U-shaped quartz reactor, the inner diameter of which
forming of CH4 . was 6 mm, at a heating rate of 10 K min−1 using a mixture
K. Takehira et al. / Journal of Catalysis 221 (2004) 43–54 45
of 3 vol% H2 /Ar as reducing gas after passing through a 13X by at a rate of 2 K min−1 from 773 to 1173 K, and finally
molecular sieve trap to remove water. A TCD was used for by keeping at 1173 for 0.5 h. The thermocouple by which
monitoring the H2 consumption. Prior to the TPR measure- the reaction temperature was controlled was placed at the
ments, the sample was heated at 573 K for 2 h in 20 vol% center of the catalyst bed. Product gases were analyzed by
O2 /N2 gas. online TCD-gas chromatography. The selectivity to CO2 ,
The Ni dispersion was determined by static equilibrium CO, or H2 was calculated based on the numbers of carbon
adsorption of H2 at ambient temperature using the pulse and hydrogen atoms in CH4 . The catalytic activity was also
method. A 20 mg of the catalyst was prereduced at 1073 K in tested by changing the space velocity between 180,000 and
H2 /N2 (5/20 ml min−1 ) flow for 30 min and cooled to am- 900,000 ml h−1 g−1 cat using 5 mg of the catalyst powders of
bient temperature in Ar atmosphere. The sample was then size less than 0.15 mm φ as dispersed in quartz wool.
used for the measurement by pulsing each 1 ml of 10 vol% When the distribution of the temperature in the catalyst
H2 /N2 . During the pulse experiment, the amount of H2 was bed was measured, 50 mg of the catalyst was dispersed with
monitored by a TCD-gas chromatograph. Uptake of H2 at 500 mg of the quartz beads and packed in the reactor placed
the monolayer coverage of the Ni species was used to esti- across horizontally by using a catalyst holder made by quartz
mate Ni metal dispersion, assuming that each surface Ni site and attached to the thermocouple sheath. The length of the
chemisorbs one hydrogen atom (H/Nisurface = 1). catalyst bed was 18 mm and the temperature was measured
by sliding the thermocouple along the catalyst bed.
2.3. Catalytic testing Also for testing the autothermal reforming of CH4 , O2 , or
H2 O was added in the CH4 /H2 O/N2 or CH4 /O2 /N2 mixed
The partial oxidation of CH4 was conducted using a gas flow, respectively, by changing the flow rate of each gas.
fixed-bed flow reactor mainly in a mixed gas flow of CH4 ,
O2 , and N2 (1/2/1 vol ratio) at 1073 K at atmospheric pres-
sure. The autothermal reforming was carried out mainly in a 3. Results and discussion
mixed gas flow of CH4 , O2 , H2 O, and N2 (2/1/2/1 vol ra-
tio). N2 gas was used as an internal standard for the analyses 3.1. Preparation of spc-Ni/MgAl catalyst
by gas chromatography. A U-shaped quartz tube reactor, the
inner diameter of which was 6 mm, was used with the cata- Metal composition, surface area, Ni dispersion, and size
lyst bed near the bottom. The catalyst particles of the size of Ni metal particles of the supported Ni catalysts are shown
0.35–0.60-mm diameter were used as dispersed in quartz in Table 1. The composition of metals was determined by
beads for the space velocity of 4800–290,000 ml h−1 g−1 cat . ICP analysis for spc-catalysts, while the value was calcu-
Usually 50 mg of the catalyst was prereduced in a gas flow lated for the imp-catalysts from the amount of raw materials,
of 20 vol% H2 /N2 by increasing the temperature at a rate of both after heating at 1123 K. The amount of Ni loading was
10 K min−1 from ambient temperature to 773 K, followed almost constant around 16 wt% on spc-catalysts. The surface
Table 1
Metal composition, surface area, and Ni dispersion of the catalysts
Catalysta Atomic Composition Ni BET surface H2 Ni Particle size
ratio for Al = 1.0b loadingb areac uptaked dispersion of Ni (nm)
(Ni + Mg)/Al Ni Mg (wt%) (m2 g−1
cat ) (µmol g−1
cat ) (%) XRD TEM
spc-Ni0.26 /Mg0.74 Al 1 0.271 0.703 16.7 124.6 253.5 17.8 7.8 7.0
spc-Ni0.38 /Mg1.62 Al 2 0.377 1.63 16.0 156.3 247.5 18.2 7.8 6.9
spc-Ni0.50 /Mg2.50 Al 3 0.488 2.52 15.8 178.6 265.1 19.7 7.0 6.1
spc-Ni0.62 /Mg3.38 Al 4 0.595 2.90 17.2 141.6 196.0 13.4 8.3 10.2
spc-Ni0.73 /Mg4.27 Al 5 0.778 3.96 17.8 125.1 203.5 13.4 8.2 12.1
spc-Ni0.85 /Mg5.15 Al 6 0.824 4.67 16.3 128.5 155.5 11.2 6.6 9.8
imp-Ni/Mg3 Al-aqe 16.3 95.4 221.5 16.0 7.2 8.3
imp-Ni/Mg3 Al-acf 16.3 54.0 66.0 4.8 16.6 22.0
imp-Ni/Mg3 Al-acacg 16.3 89.2 139.3 10.0 16.7 18.6
imp-Ni/α-Al2 O3 16.3 8.2 48.6 3.5 31.1 35.5
imp-Ni/γ -Al2 O3 16.3 106.3 122.9 8.9 11.4 13.0
imp-Ni/MgO 16.3 17.2 13.8 1.0 − 8.2
a Reduced at 1173 K for 0.5 h in H2 /N2 (5/20 ml min−1 ).
b Determined by ICP analysis for spc-catalysts after calcination at 1123 K for 5 h and calculated for imp-catalysts.
c Calcined at 923 K for 14 h and at 1123 K for 5 h.
d Determined by H2 pulse method.
e Impregnated in aqueous solution of Ni(II) nitrate.
f Impregnated in acetone solution of Ni(II) nitrate.
g Impregnated in acetone solution of Ni(II)-acac.
46 K. Takehira et al. / Journal of Catalysis 221 (2004) 43–54
Table 2
Effect of the reduction conditions on the Ni dispersion of the catalysts
Catalyst Reduction H2 Ni
conditionsa uptakeb dispersion
(µmol g−1
cat ) (%)
spc-Ni0.5 /Mg2.5 Al 1023 K for 0.5 h 83.8 6.2
spc-Ni0.5 /Mg2.5 Al 1073 K for 0.5 h 221.8 16.5
spc-Ni0.5 /Mg2.5 Al 1123 K for 0.5 h 244.9 18.2
spc-Ni0.5 /Mg2.5 Al 1173 K for 0.5 h 265.1 19.7
a Reduced in H /N (5/20 ml min−1 ).
2 2
b Determined by H pulse method.
2
Fig. 2. TEM images of the supported Ni catalysts after reduction. (a) spc-Ni0.26 /Mg0.74 Al; (b) spc-Ni0.32 /Mg1.62 Al; (c) spc-Ni0.5 /Mg2.5 Al; (d) spc-
Ni0.62 /Mg3.38 Al; (e) spc-Ni0.73 /Mg4.27 Al; (f) spc-Ni0.85 /Mg5.15 Al; (g) imp-16.3wt%Ni/Mg3 Al-ac; (h) imp-16.3wt%Ni/Mg3 Al-acac.
face catalyzes the combustion of CH4 to form CO2 and at the high space velocity (9 × 105 ml h−1 g−1cat ) corresponds
H2 O, but does not catalyze the reforming reactions of CH4 to that of 1 wt% Rh/MgO reported as the best Rh catalyst
with H2 O and CO2 to CO and H2 , resulting in a substan- by Ruckenstein and Wang [4]. Either increasing or decreas-
tial decrease in the CH4 conversion. The partial oxidation ing in the Mg/Al ratio from the value of 1/3 resulted in a
of CH4 (1) on Ni catalysts is generally composed of an decrease in the CH4 conversion with increasing the space
exothermic combustion (2) and two endothermic reforming velocity. Lower ratios of the Mg/Al, e.g., 1/1, afforded
reactions (3) and (4) under the conditions of CH4 /O2 = 2/1: segregation of the Al(OH)3 phase from Mg–Al hydrotal-
cite during the co-precipitation, while higher Mg/Al ratio
1
4 CH4 + 12 O2 → 14 CO2 + 12 H2 O resulted in the formation of a MgO-rich phase after the
−1
K = −801 kJ mol ,
0
H298 (2) calcination. The former hindered the formation of a well-
crystallized hydrotalcite phase, and the latter strongly held
1
2 CH4 + 12 H2 O → 12 CO + 32 H2 Ni in the MgO structure as the solid solutions by lacking the
−1 moderation effects due to the Al3+ incorporation. It is likely
K = +206 kJ mol ,
0
H298 (3)
that both cases suppressed the formation of highly dispersed
4 CH4 + 4 CO2 → 2 CO + 2 H2
1 1 1 1
Ni metal particles, resulting in the lowering of the activity at
−1
K = +247 kJ mol .
0
H298 (4) the high space velocity.
The combustion proceeds more rapidly than the latter two
3.7. Temperature of the catalyst bed in partial oxidation of
reforming reactions and the rates of the latter reactions con-
CH4
siderably depend on the activity of the Ni catalyst used. If
the combustion of CH4 alone takes place over the Ni cat-
When the rates of reforming reactions are slow, the heat
alyst, the CH4 conversion can be calculated as 1/4 = 25%
of combustion may be accumulated in the catalyst bed, re-
under the gas composition of CH4 /O2 = 2/1. However, the
sulting in the formation of a hot spot. On the other hand, if
CH4 conversion remained at values above 25% over all the
we can provide a catalyst of high performance for the re-
powder catalysts tested at the high space velocity. It is likely
forming, the heat of combustion may be quickly eliminated
that certain equilibrium between the oxidized and the re-
from the catalyst bed by the following reforming reactions
duced states was attained on the surface of Ni particles of
and therefore no accumulation of the heat appears. The high-
the catalyst, and the latter surface still catalyzed the reform-
est temperature was observed at the inlet of the catalyst bed,
ing reactions, though poorly, over imp-catalysts.
where the heat accumulation mainly occurred by the com-
The behaviors of spc-Ni/MgAl catalysts of various
bustion. The highest temperatures of the catalyst bed were
Mg/Al ratios were also tested in the partial oxidation of CH4
measured by changing the space velocity from 20,000 to
by changing the space velocity (Fig. 8), the highest activ-
90,000 ml h−1 g−1cat on the supported Ni catalysts (Fig. 9).
ity among which was still obtained over spc-Ni0.5 /Mg2.5 Al
A blank test with quartz wool alone instead of the catalyst
with the highest Ni dispersion (Table 1). High activity of
afforded a constant temperature covering all the space ve-
spc-Ni0.5 /Mg2.5 Al proved by the high CH4 conversion even
locities. Actually less than 5% of CH4 was consumed by
the combustion reaction, resulting in no substantial heat ac-
Fig. 8. The partial oxidation of CH4 over spc-Ni/MgAl cata- Fig. 9. Temperature at the inlet of the catalyst bed in the partial oxida-
lysts. (a) spc-Ni0.26 /Mg0.74 Al; (b) spc-Ni0.32 /Mg1.62 Al; (c) spc-Ni0.5 / tion of CH4 . (a) spc-Ni0.26 /Mg0.74 Al; (b) spc-Ni0.32 /Mg1.62 Al; (c) spc-
Mg2.5 Al; (d) spc-Ni0.62 /Mg3.38 Al; (e) spc-Ni0.73 /Mg4.27 Al; (f) spc- Ni0.5 /Mg2.5 Al; (d) spc-Ni0.62 /Mg3.38 Al; (e) spc-Ni0.73 /Mg4.27 Al; (f) spc-
Ni0.85 /Mg5.15 Al; (g) thermodynamic equilibrium. A mixed gas of CH4 / Ni0.85 /Mg5.15 Al. A mixed gas of CH4 /O2 /N2 = 2/1/1 was used at
O2 /N2 = 2/1/1 was used at 1073 K for 5 mg of the catalyst diluted by 1073 K for 50 mg of the catalyst diluted by 500 mg of quartz beads. A length
quartz beads. of the catalyst bed was 18 mm.
52 K. Takehira et al. / Journal of Catalysis 221 (2004) 43–54