INTERNATIONAL JOURNAL OF ENERGY RESEARCH

Int. J. Energy Res. 2013; 37:1896–1907

Published online 10 January 2013 in Wiley Online Library (wileyonlinelibrary.com). DOI: 10.1002/er.3009

Hydrogen-rich gas production from ethanol steam-

reforming reaction using NiZr-loaded MCM-48 catalysts
at mild temperature
Jun Su Lee1, Dongjin Kim1, Byung-Hyun Choi2 and Misook Kang1,*,†
1
Department of Chemistry, College of Science, Yeungnam University, Gyeongsan, Gyeongbuk, 712-749, Republic of Korea
2
Korean Institutes of Ceramic Engineering and Technology (KICET), Geumcheon-gu, Seoul 153-801, Republic of Korea

SUMMARY
The rich-hydrogen generation from ethanol steam reforming over NiZr, which is used as an anode material in solid oxide
fuel cells, -loaded MCM-48 (NiZr/MCM-48) catalyst was investigated in this study. We used an impregnation approach to
synthesize an MCM-48 (70.0 wt-%) support loaded with bimetallic NiZr (30.0-wt%, Ni:Zr atomic ratio = 4:6, 5:5, and 6:4),
and the prepared catalysts were applied to the steam-reforming reactions of ethanol. These three bimetallic NiZr/MCM-48
catalysts exhibited significantly higher reforming reactivity than the mono-metal, Ni-loaded MCM-48 (Ni/MCM-48)
catalyst. The hydrogen production was started from 350
C over the three NiZr/MCM-48 catalysts, compared to above
550
C over the Ni/MCM-48 catalyst. The catalytic performance was affected by the Zr content. The H2 production
and ethanol conversion were maximized at 85% and 95%, respectively, over Ni4Zr6/MCM-48 at 750
C for 1 h at
CH3CH2OH:H2O = 1:1 and a gas hourly space velocity of 4000 h-1. This high performance was maintained for up to
60 h. Copyright © 2013 John Wiley & Sons, Ltd.
KEY WORDS
hydrogen production; ethanol steam-reforming reaction; NiZr/MCM-48

Correspondence
*Misook Kang, Department of Chemistry, College of Science, Yeungnam University, Gyeongsan, Gyeongbuk, 712–749, Republic of Korea.
†
E-mail: mskang@ynu.ac.kr

Received 10 September 2012; Revised 28 November 2012; Accepted 30 November 2012

1. INTRODUCTION higher than that of methanol or dimethyl ether, making

The processes for converting petroleum fuels into hydrogen-
rich gas products include steam reforming [1], partial
oxidation [2], auto thermal reforming [3], dry reforming
[4], and a combination of two or more [5]. Steam reform-
ing has the highest efficiency for hydrogen production.
Gaseous hydrocarbons can reduce the catalyst life and
degrade the performance of the hydrogen production
because of the catalytic poison that results from the CO
generation during the oxidation reaction. To solve these
problems, methanol [6], acetic acid [7], and dimethyl
ether [8], which including rich-oxygen, have been used
as raw materials in the manufacture of hydrogen. These
are completely oxidized to CO2 during the reforming
reaction, and the reformation of ethanol in the presence
of steam has been a general practice for hydrogen
production.
Recently, ethanol has been used for steam reforming [9]
because of its non-toxicity and ease of transport and
storage. However, the oxidation temperature of ethanol is
its decomposition difficult. This method offers the
advantage of producing more hydrogen per mole of
ethanol that is reformed because hydrogen can also be
extracted from the steam. On the other hand, Ni-based
Al2O3 support catalysts [10,11] have been used for ordi-
nary steam-reforming processes because of their accept-
ably high activity and significantly lower cost than the
alternative precious metal-based catalysts [12]. However,
Ni-based Al2O3 support catalysts are susceptible to deacti-
vation resulting from the deposition of carbon, even
when operating at steam-to-carbon ratios predicted to be
thermodynamically outside of the carbon-forming regime.
Additionally, an especially serious problem in NiAlO4
catalysts is the abrupt catalytic deactivation that occurs at
high temperatures above 650
C, due to the formation of a
NiAlO3 spinal structure resulting from the strong sintering
between Ni and Al, and this deactivation leads to reactor
shutdown and the reversal of the feed gases [10,11]. To
overcome these problems, many researchers have used the
non-nickel-based and non-alumina supported catalysts for

1896 Copyright © 2013 John Wiley & Sons, Ltd.

Hydrogen-rich gas production from ethanol steam reforming
application to ethanol steam reforming [13,14]. However,
some problems remain in terms of the catalytic activity
and lifetime.
We herein have tried the introduction of the Zr
component with the capability for hydrocarbon cracking,
hydrogen attraction from hydrocarbons, and depressing
the sintering between Ni and the support added between
them, as a catalytic active site in ethanol steam-reforming
reaction. Ni-loaded yittrium stabilized zirconia has been
widely used as an anode materials in solid oxide fuel
cells. The material has a high conductivity at high temper-
ature and endurances for hydrogen reduction and CO
poison [15]; therefore, the hydrogen production will be
improved by introduction of Zr component into an active
site of the catalyst for ethanol steam reforming. Moreover,
we use MCM-48 with high meso-porosities and consisting
of a silica framework with no Al component as a support
to eliminate the catalytic deactivation resulting from
the strong sintering between Ni and Al. Therefore, in this
study, we prepare the NiZr-loaded MCM-48 catalysts
for application into ethanol steam reforming. The ethanol
steam-reforming reactions are conducted in the tempera-
ture range of 300–800
C at intervals of 50
C. The physico-
chemical properties of the catalysts were determined by
X-ray diffraction (XRD), transmission electron microscopy
(TEM), H2-temperature-programmed reduction (TPR), and
X-ray photon spectroscopy (XPS) analyses.
2. EXPERIMENTAL SECTION
2.1. Preparation of MCM-48 support and
NiZr/MCM-48 catalysts
For the preparation of MCM-48 (70.0 wt-%) catalysts
with various loadings of NiZr (30.0 wt-%, Ni:Zr atomic
ratios =4:6, 5:5, and 6:4), MCM-48 mesoporous material
was hydrothermally synthesized from the assembly of cetyl-
trimethylammonium bromide (CTAB) and Ludox HS40
with NaOH. The general preparation method of MCM-48
is reported elsewhere [16]. Briefly, solution A is a mixture
containing Ludox HS40 (SiO2 sol 40.0 wt-%, DuPont Co.,
USA) as a Si precursor, NaOH, and distilled H2O. The mix-
ture was stirred for 2 h at 80
C. Solution B consisted of a
mixture of CTAB (Junsei Co., Japan), distilled H2O, and
ethanol. Solution B was added to solution A slowly. After
continuous stirring for 2 h at room temperature, the final
gel solution was transferred to an autoclave and heated at
140
C for 16 h. The resulting as-synthesized solid product
was obtained by filtration, dried in air, and calcined at
550
C for 3 h to obtain the porosity. The three NiZr/
MCM-48 catalysts were obtained using an impregnation
method. Nickel and zirconium nitrate (Ni(NO3)2 and Zr
(NO3)4, 99.9%, Junsei Co., Japan), as precursors of the Ni
and Zr components, were added at an atomic ratio and
were simultaneously dropped into 25.0 ml of ethanol
including MCM-48 powder. The slurry was stirred
for 2 h, evaporated at 50
C for 3 h, and thermally treated
Int. J. Energy Res. 2013; 37:1896–1907 © 2013 John Wiley & Sons, Ltd.
DOI: 10.1002/er
J. S. Lee et al.
at 550
C for 2 h in air. Finally, the following four
experimental catalysts were prepared for comparison:
Ni(30.0 wt-%)/MCM-48(70.0 wt-%), Ni4Zr6/MCM-48,
Ni5Zr5/MCM-48, and Ni6Zr4/MCM-48 with various Ni
and Zr contents.
2.2. Characterizations of the NiZr/MCM-48
catalysts
The four prepared experimental catalysts were identified
through powder XRD (MPD model, PANalytical, Yeungnam
University Instrumental Analysis Center, Korea) analysis
with nickel-filtered Cu Ka radiation (30 kV, 30 mA) at 2-theta
angles of 10–100o. The scan speed was 10o/min, and the
time constant was 1 s. The shapes and surface atomic
compositions of the particles of the four experimental
catalysts were determined by field emission scanning elec-
tron microscopy (S-4100, Hitachi, Yeungnam University
Instrumental Analysis Center, Korea)/energy dispersive
spectroscopy (EDS-EX-250, Horiba) operated at 120 kV.
The pore sizes and shapes of the MCM-48 particles were also
measured by TEM (H-7600, Hitachi) operated at 120 kV.
The Brunauer, Emmett, and Teller (BET) surface area was
measured using a Micrometrics ASAP 2000 instrument.
Before BET surface measurement, the three bimetallic
Ni-Zr-loaded catalysts were degassed under vacuum at
120
C for 12 h, and then thermally treated at 300
C for 30
min. The BET surface areas of the catalysts were measured
by nitrogen gas adsorption using a continuous flow method
with a mixture of nitrogen and helium as the carrier gas.
XPS measurements of Ni2p, Zr3d, Si2p, C1s, and O1s were
recorded with a model ESCALAB250 XPS system (Thermo
Fisher Scientific (U.K), Busan Center, Korea Basic Science
Institute, Korea), equipped with a non-monochromatic Al
Ka (1486.6 eV) X-ray source. The powders were pelletized
at 1.2  104 kPa for 1 min, and the 1.0-mm pellets were
then maintained overnight in a vacuum (1.0  10–7 Pa) to
remove any water molecules from the surface prior to the
measurement. The base pressure of the system was
below 1  10–9 Pa. The experiments were conducted with a
15kV and 150-W source power and an angular acceptance
of 5º. The analyzer axis made an angle of 90º with the
specimen surface. A Shirley function was used to subtract
the background in the XPS data analysis. The Ni2p, Zr2p,
Si2p, C1s, and O1s signals were fitted using mixed
Lorentzian– Gaussian curves. H2-TPR was conducted as
follows. About 0.3 g of the four experimental catalysts was
pre-treated under helium flow (30 ml/min) at 700
C for 2 h
and then cooled to room temperature. The analysis was
carried out by flowing 30 ml/min of H2 (10 vol. %)/N2
and raising the temperature of the catalyst from room temper-
ature to 700
C at 5
C/min. The change in the hydrogen
concentration was measured with a gas chromatograph (GC
series 580, GOW-MAC) equipped with a thermal conductiv-
ity detector (TCD). In order to study the formation of carbon
species on the catalyst surface, temperature-programmed
oxidation (TPO) was performed using the TGA N-1000
instrument by introducing high purity oxygen gas into the
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J. S. Lee et al.
system after purging it with N2. A 7.0 mg sample was placed
in a sample pan and heated from 50 to 900
C at a constant
heating rate of 10
C/min. High purity O2 gas was flowed at
20 ~ 40 ml/min into the TPO system to combust the carbon
accumulated on the catalyst after the reaction. The profiles
were obtained in the same manner as that described for
TPR, and the coke contents were calculated from the weight
loss in the temperature range from 50 to 900
C.
2.3. Ethanol steam reforming over NiZr/MCM-
48 catalysts
Figure 1 shows the reactor for the ethanol steam reforming,
and the catalytic activities of the four experimental catalysts
were measured in the temperature range for 300–800
C for
1 h reaction time intervals at steam-to-ethanol ratios of 1:1,
1:2, and 1:3 with gas hourly space velocities (GHSV) of
3000, 4000, and 6000 h-1. The three bimetallic NiZr-loaded
catalysts (0.4 g) were pelletized to 20–24 mesh and then
packed with a small amount of quartz wool to prevent their
movement in the fixed bed quartz reactor, which was verti-
cally mounted inside the furnace. An ethanol/water solution
(mol/mol) was then introduced into the vaporizer. Typically,
according to most articles [16,17], the ethanol and water
were mixed at a desired weight percentage and vaporized
immediately at a boiling point temperature before the
mixture was sent to the reactor. However, in this study, the
amount of steam was adjusted by regulating the temperature,
according to the following partial pressure law, as described
in detail in a previous paper [17]. Here, the vaporization
temperatures were affected by the ethanol and steam
concentrations. The flow rate was held constant at a rate of
Figure 1. Apparatus of the catalytic reactor used for ethanol steam reforming.
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Hydrogen-rich gas production from ethanol steam reforming
10 and 30 ml/min for ethanol and steam, respectively. Argon
gas was used to transport the vaporized mixture to the reac-
tor. The reaction products were measured using on-line GC
on a Donam DS6200 (Donam company, Korea) that was
equipped with a TCD and a flame ionizing detector (FID).
The TCD was used to detect H2, CH3CHO, C2H5OH, CO,
and CO2, and the FID to detect CH4, C2–C5 hydrocarbons,
and other products. The ethanol conversion (XEtOH) and
the selectivity of the C-containing products (SC) of the vari-
ous samples were calculated using the following equations:
XEtOH ¼ ðmol EtOHin  mol EtOHout Þ=mol EtOHin x 100%
SCH2 ¼ mol H2 =½ðmol EtOHin  mol EtOHout Þ  ðmol H2 Oin
mol H2 Oout Þ x 100%
SCothers ¼ mol othersout =ðmol EtOHin  mol EtOHout Þ x 100%
In this study, GHSV was calculated based on the total flow
rate of the feed mixture in the gas phase.
3. RESULTS AND DISCUSSION
3.1. Characteristics of the four
experimental catalysts
The four experimental catalysts were characterized by XRD
before the reaction. The XRD patterns are shown in Figure 2.
The diffraction lines of the NiO phase at 2-theta angles of
around 37.27o, 43.29o, 62.89o, 75.44o, and 79.43o could be
seen in the XRD patterns of all the catalysts, corresponding
to the (d111), (d200), (d220), (d311), and (d222) spaces, respec-
tively. They were ascribed to the cubic structure and assigned
Int. J. Energy Res. 2013; 37:1896–1907 © 2013 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Hydrogen-rich gas production from ethanol steam reforming
Figure 2. XRD patterns of the four experimental catalysts
before ethanol steam reforming.
to JCPDS card No. 78–0643. The special peaks decreased
with increasing concentration of loaded Zr. The diffraction
lines of the ZrO2 phase at 2-theta angles of around 30.27o
(d101), 35.24o (d110), 50.37o (d112), and 60.19o (d211)
could be also exhibited in the XRD patterns of the three
bimetallic NiZr-loaded catalysts, which have indicated the
tetragonal structure assigned to JCPDS card No. 88–1007.
The special peaks were broad with increasing concentration
of loaded Ni. However, the peak corresponding to NiZr alloy
was not observed in this study. Conversely, the line widths of
the peaks were broad, which generally indicates a smaller
Table I. Atomic compositions calculated from the EDS analysis for the four experimental catalysts.
Catalysts/elements O Ni
Ni/MCM48 76.04
Ni4Zr6/McM48 61.69
Ni5Zr5/McM48 61.84
Ni6Zr4/McM48 65.60
Int. J. Energy Res. 2013; 37:1896–1907 © 2013 John Wiley & Sons, Ltd.
DOI: 10.1002/er
J. S. Lee et al.
crystalline domain size. The full width at half maximum
(FWHM) height of the peaks at 2 theta = 43.29o (d200) and
30.27o (d101) of NiO and ZrO2, respectively, were measured.
The Scherrer equation, t = 0.9l/bcosθ, where l_ is the wave-
length of the incident X-rays, b_ the FWHM in radians, and θ_
the diffraction angle, was used to determine the crystalline
domain size. The calculated crystalline domain sizes based
on a special peak of 43.29o (d200) of NiO were 23.24,
18.08, 21.67, and 29.59 for Ni/MCM-48, Ni4Zr6/MCM-48,
Ni5Zr5/MCM-48, and Ni6Zr4/MCM-48, respectively. In the
same way, the crystalline domain sizes at 30.27o (d101) over
the NiZr/MCM-48 samples were 4.68, 3.13, and 7.84 nm,
referred to as b), c), and d), respectively. The smaller grain
sizes indicated that the Ni and Zr ingredients were well
dispersed in the MCM-48 support.
In Table I, the EDS analysis (atomic composition)
revealed variation in loaded metal concentrations, with
the Ni and Zr surface concentrations being relatively
higher and lower, respectively. The atomic ratios of each
metal component in Ni:Zr were 4.42:6.21, 6.71:5.70, and
7.63:5.31 in Ni4Zr6/MCM-48, Ni5Zr5/MCM-48, and
Ni6Zr4/MCM-48, respectively. However, the amounts of
Ni and Zr presented on the surface were not greatly
affected by the amount inserted during synthesis, which
also indicated high dispersion.
The pore size and shapes of the four experimental
catalysts were characterized using the TEM images shown
in Figure 3. The observed mesopores with regular hexago-
nal form were not clear because the NiZr/MCM-48 cata-
lysts were covered by Ni and Zr components compared
to the unique mesoporous MCM-48. The black spots of
cubic and spherical shapes, which were considered to be
Zr Si
6.77 - 15.80
4.42 6.21 27.68
6.71 5.70 25.69
7.63 5.31 21.45
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J. S. Lee et al.
Figure 3. TEM images of the four experimental catalysts before ethanol steam reforming.
aggregated NiO particles, were observed on the external
surface of the mesopores in MCM- 48, and the size of these
particles increased from 50 to 70 nm with increasing Ni
mole fraction.
The pore size distribution is an important characteristic
for porous materials. Among these methods, Barrett-Joyner-
Halenda plots are a suitable method for the range of
mesopores [18]. The relative pressure at which pore filling
takes place by capillary condensation can be calculated from
Kelvin’s equation. By using Kelvin’s equation, the pore
radius in which the capillary condensation occurs actively
can be determined as a function of the relative pressure
(P/P0). The mean pore diameter, Dp, was calculated from
Dp = 4VT/S, where VT is the total volume of pores, and S
the BET surface area. Figure 4 shows the adsorption–
desorption isotherms of N2 at 77 K for the four mesopor-
ous catalysts. They illustrate the shape and behavior of
the N2 adsorption isotherms for the mesoporous materials.
All the isotherms belonged to IV type in the IUPAC
classification [19] in all samples. The isotherms were
wide, without any clear plateau, and a certain hysteresis
1900
Hydrogen-rich gas production from ethanol steam reforming
slope was observed at intermediate and high relative pres-
sures in all four catalysts, which is indicative of the pres-
ence of large mesopores.
In Table II, the average pore diameter value, Dp, ranged
from 3.47 to 6.85 nm, and the pore size decreased with
increasing Zr content. The adsorption and desorption lines
for the four experimental catalysts overlapped completely
in the low relative pressure range, while the hysteresis loop
was in the high relative pressure region (P/P0 0.49 ~ 0.85),
mainly due to the presence of bottle types of pore. These
bottle pore types had a larger pore size in the bottle body,
which induced hysteresis in the high relative pressure
region. The BET surface areas in the three NiZr/MCM-
48 catalysts were not greatly decreased compared to the
value of 560 m2/g for pure MCM-48, and their surface areas
were in the range of 403–463 m2/g; however, it was dramat-
ically decreased in Ni/MCM-48 to 80.97 m2/g, which attrib-
uted to the sintering of Ni.
The H2–TPR profiles of the four experimental catalysts
are shown in Figure 5. The changes corresponding to the
reduction of the NiO/Ni [20] components in the four
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Hydrogen-rich gas production from ethanol steam reforming J. S. Lee et al.

Figure 4. Adsorption-desorption isotherm curves of the four experimental catalysts.

Table II. BET surface areas and pore diameters determined by adsorption-desorption isotherm curves for the four experimental catalysts.

Catalysts BET specific surfacearea(m2/g) Total pore volume(p/p0 = 0.009) Pore diameter(nm)

Ni/MCM48 80.97 0.14 6.85

Ni4Zr6/McM48 403.63 0.37 3.62
Ni5Zr5/McM48 463.76 0.40 3.47
Ni6Zr4/McM48 449.78 0.40 3.56

experimental catalysts were observed in the H2–TPR

profiles. In general, the H2–TPR results indicated that
the peak area corresponds to the hydrogen uptake and the
peak at high temperatures corresponds to the catalytic
reaction involved in the reduction mechanism. A reduction
type for the Ni component was seen in all four catalysts at
300–400
C, which was considered to be NiO/Ni. The
reduction peak of the Ni oxides was gradually shifted to
lower temperatures with increasing Zr content, and the great-
est reduction was observed in the cases of Ni4Zr6/MCM-48
and Ni6Zr4/MCM-48. Otherwise, the reduced peak of ZrO2
to ZrO was not shown in this study.

3.2. Ethanol steam-reforming reaction over

the four experimental catalysts

Ethanol steam reforming was carried out with 0.5 g of

Figure 5. H2-TPR curves of the four experimental catalysts. each of the four experimental catalysts under the reaction

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J. S. Lee et al.
conditions of temperature = 300–800
C, GHSV = 4,000 h1,
and H2O/EtOH = 1.0. Figure 6 compares the time-on-stream
activity of the four experimental catalysts. In (b), in which
only the ethanol conversion is compared, the conversion
over the Ni/MCM-48 catalyst was higher than those of
the three NiZr/MCM-48 catalysts, which was attributed to
the methanation of carbon dioxide and carbon monoxide
on the Ni, as previously reported [10,11]. Particularly, the
ethanol conversions over Ni/MCM-48 and Ni4Zr6/MCM-
48 catalysts were maximized at 98% at 800
C. On the
other hand, the hydrogen production gradually increased
over the three NiZr/MCM-48 catalysts as the temperature
was increased from 350 to 750
C, to a maximum of 85%
at 750
C over Ni4Zr6/MCM-48. Otherwise, the starting point
for hydrogen evolution was shifted to the higher temperature
of 500
C over the Ni/MCM-48 catalyst in spite of the higher
ethanol conversion. The Ni4Zr6/MCM-48 catalyst provided a
significantly higher reforming reactivity than the conven-
tional Ni-based MCM-48 catalyst. This suggested that the
Zr particles prevented sintering between the Ni particles
and was further attributed to a synergy effect between Ni
and Zr. Here, five species were present in the product
distribution: H2, CO2, CO, CH4, and feed CH3CH2OH.
Possibly, the conversion of ethanol to hydrocarbons like
C3–C5 prevailed over the hydrogen synthesis at the lower
temperature of 200–350
C, and the reaction products were
transferred to CH4, H2, and CO2 at the medium temperature
of 400–550
C. Finally, the synthesis of hydrogen from
ethanol steam reforming prevailed over the hydrocarbon
synthesis at the higher temperature of 600–800
C, and the re-
action products were distributed in the ratio of 40–85% H2:
below 10–15% CH4 and CO2. Most importantly, the CO
selectivity approached zero percent over the whole tempera-
ture range, and the CH4 production was slightly increased
compared to that over the catalysts loaded only with Ni.
Therefore, our results demonstrated the synergistic effect of
Figure 6. (a) H2 production and (b) ethanol conversion over the four experimental catalysts according to the reaction temperature.
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Hydrogen-rich gas production from ethanol steam reforming
the introduction of Zr between the Ni and the MCM-48
support on the catalytic performance and the decreased
sintering phenomenon and the consequently reduced
catalytic deactivation.
Figure 7a and b shows the catalytic performances for
the ethanol steam-reforming reaction over the Ni4Zr6/
MCM- 48 catalyst at various GHSV values and with
various ethanol/steam concentrations, diluted in argon gas
of 30 vol-percent. The H2 production was positively corre-
lated with GHSV as the reaction temperature exceeded
350
C, with an ethanol conversion exceeding 85% over
the entire GHSV range, as shown in figure a. The efficien-
cies of the ethanol conversion and hydrogen production
were both reduced with decreasing GHSV below 3000
and increasing GHSV above 6000 over the complete
temperature range. Therefore, the optimal reaction condi-
tions according to the active response for the production
of H2 over the Ni4Zr6/MCM-48 catalyst were a GHSV of
4000 h1, an ethanol steam concentration ratio of 1:1
(30 vol-percent), and a reaction temperature of 750
C. In
figure b, the optimal conditions corresponded to an EtOH:
H2O ratio of 1:1, and 85% of the hydrogen was emitted at
750
C, with an ethanol conversion of 95%. However, the
ethanol conversion was dramatically decreased at higher
water concentrations at an EtOH: H2O ratio of 1:3, in spite
of the high ethanol conversion of 99%. FID-GC investigation
revealed that methane and other light hydrocarbons (~C4)
were produced with high water molecules, possibly because
the H ions in H2O act as Brønsted acidic sites.
3.3. Characteristics of catalysts after
ethanol steam reforming
Figure 8 compares the XRD patterns of the four experimen-
tal catalysts after 10 h of reaction at 750
C. The diffraction
lines of the Ni metal phase shown at 2-theta angles of
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Hydrogen-rich gas production from ethanol steam reforming
Figure 7. Ethanol conversion and H2 production according to the (a) GHSV and (b) ethanol/steam ratio over Ni4Zr6/MCM-48.
Figure 8. Comparison of XRD patterns for the four experimental
catalysts before and after ethanol steam-reforming reaction.
44.49o (d111) and 51.85o (d420) [JCPDS#87-0712] were
clearly different after the reaction in all four catalysts,
and the peaks assigned to Ni oxides were smaller than
before reaction. This indicated that the Ni components
acted as active sites in the ethanol steam-reforming reaction.
The ZrO2 peak decreased after the reaction, which automat-
ically implied a comparison with before the reaction, and the
trend was particularly pronounced in the Ni4Zr6/MCM-48
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J. S. Lee et al.
Figure 9. Comparison of XPS curves for Si2p, Zr3d, Ni2p, and
O1s orbital of two catalysts, (a) Ni/MCM-48 and (b) Ni4Zr6/
MCM-48, before and after ethanol reforming reaction.
catalyst. Additionally, the peaks of the Zr metal phases
appeared after the reaction at 2-theta angles of 25.44o
(d110) and 35.78o (d110) [JCPDS #34-0657]. This
result confirmed that the Zr component also acted as an
active site in the ethanol steam-reforming reaction, as
with Ni.
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J. S. Lee et al.
Figure 9 compares the typical survey and high-resolution
spectra obtained from the quantitative XPS analyses of the
two catalysts, Ni/MCM-48 and Ni4Zr6/MCM-48, before
and after ethanol steam reforming. The survey spectra of
the particles contained Zr3d, Ni2p, Si2p, and O1s peaks, which
were analyzed based on an XPS handbook [21]. The Si2p3/2
spin–orbital photoelectron, which was assigned to the Si
component in the MCM-48 support, was located at a binding
energy of 103.3 eV. The peak in Ni/MCM-48 was not
changed after the reaction compared to that before reaction;
however, the binding energy curve for the Si2p3/2 exhibited
a lower energy of 102.0 eV in Ni4Zr6/MCM-48, and the peak
was shifted to a higher binding energy after reaction. In
general, a large binding energy indicates a more oxidized
state. The same phenomenon occurred for O1s (at 531.5 eV
(hydroxides) for Ni/MCM-48), which was distributed at
529.0 eV for the Ni4Zr6/MCM-48 assigned to metal oxides,
and it also shifted to a higher energy after reaction. These
results indicated that the Si and O ions were oxidized to
higher oxidation states after the ethanol reforming and
confirmed the involvement of the Si and O ions in the reduc-
tion of ethanol or other hydrocarbons that were evolved
during the ethanol-reforming reaction to afford the produc-
tion of H2 or hydrocarbons in Ni4Zr6/MCM-48. On the other
hand, the Zr3d region in Ni4Zr6/MCM-48 was decomposed
into two contributions, which were assigned to Zr3d5/2 and
Zr3d3/2 at 181.5 and 183.0 eV in ZrO2, respectively [21].
The oxidation state was divided into three types after
reaction, and the values were smaller after the reaction.
Generally, the same phenomenon occurred for Ni2p3/2 and
Ni2p1/2 at binding energies of 853.8 and 871.29 eV, which
were assigned to NiO [21]. In this study, Ni2p3/2 and Ni2p1/2
were also expressed at 853.5 and 871.0 eV, respectively, in
Figure 10. (a) TPO profiles and (b) XPS curve of C1s of the four experimental catalysts after ethanol reforming reaction.
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Hydrogen-rich gas production from ethanol steam reforming
both samples before and after reaction. However, the peak
intensities were largely decreased with no change of peak
position after reaction, particularly in Ni4Zr6/MCM-48. This
indicated that the Ni components acted as a strong catalyst
for the ethanol steam reforming and then deactivated. These
results indicated that the Zr oxidation state was changed after
the ethanol reforming and, consequently, confirmed that the
Zr ions were involved in the reduction of ethanol or other
hydrocarbons such as Ni ions that were evolved during the
ethanol-reforming reaction to afford the production of CH4
from CO or CO2 molecules.
To determine the amount of carbon deposited on the
catalysts, we carried out TPO measurement (a) and C1s
XPS analysis (b), as shown in Figure 10. The deposited
amount (peak area) and species of carbons (decomposed
temperature) are closely related to the catalytic deactivation.
Generally, the extent of catalytic deactivation is reduced
when a smaller amount of carbon is deposited. When the
Ni-only component was exposed to the outside surface of
the Ni/MCM-48 sample, the deposited carbons underwent
greater oxidation at high temperatures of 530
C, indicat-
ing the deposition of heavy carbons. Similar amounts
of carbon were deposited in the Ni6Zr4/MCM-48 and
Ni5Zr5/MCM-48 catalysts, but the peak areas were
smaller in the latter, whereas the deposited carbon amount
was the smallest in Ni4Zr6/MCM-48. We therefore
concluded that the Zr addition helped to retain the stability
of the Ni crystallites and avoided their conglomeration in
the ethanol steam-reforming reaction, which corresponds
to the better stability demonstrated by the three NiZr/
MCM-48 catalysts compared with Ni/MCM-48. On
the other hand, although one C1s orbital is generally seen
at 284.5 eV for bulky carbons [21], the peak presented
Int. J. Energy Res. 2013; 37:1896–1907 © 2013 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Hydrogen-rich gas production from ethanol steam reforming
in this study could be split into three peaks at around
281.0, 283.2-284.8, and 288.2 eV, due to the mixture of
carbide, carbon, and carboxyl species in the coke deposi-
tion over the catalyst. Compared to over Ni/MCM-48,
the carbon and carboxyl species were strongly seen in
Ni4Zr6/MCM-48.
In an interesting result shown in Figure 11, a carbon lump
was found after ethanol steam reforming over the four exper-
imental catalysts and was observed by TEM. At a certain
time after the beginning of the reaction, e.g. 10 h at 750
C,
the carbons were deposited on the surface of the catalyst. In
general, CO2 and ethanol could be converted into carbon
nanotubes (or filaments) on the carbon deposited on the
catalyst surface. As we have suggested above, a molecule
of ethanol was dissolved into two molecules of CO and H2
as intermediates, and subsequently converted at higher
temperatures to pure carbon. The hydrogen and oxygen
may have disappeared due to reaction with the main metal
Figure 11. TEM images of deposited carbon over the four experimental catalysts after ethanol steam reforming.
Int. J. Energy Res. 2013; 37:1896–1907 © 2013 John Wiley & Sons, Ltd.
DOI: 10.1002/er
J. S. Lee et al.
oxides, in the absence of any kind of metal or other catalyst
capable of functioning. Finally, the carbons react with H2
and are transferred into C = C molecules, which can be a
precursor of carbon nanofilaments or tubes [22], as we may
infer from some CH4 evolution during the ethanol cracking.
Interestingly, many carbon lumps were generated in the
catalysts with high Ni content; otherwise, the carbon
nanotubes increased with increasing Zr content, particularly
in Ni4Zr6/MCM-48.
Finally, the catalytic deactivation was tested for the
Ni4Zr6/MCM-48 catalyst, and the results are shown in
Figure 12. In a dramatic result, the H2 production exceeded
76–64% mol with above 95% ethanol conversion depend-
ing on the presence of Zr. The catalyst lifetime was greatly
improved in the Ni4Zr6/MCM-48 catalyst compared to that
of the catalyst without Zr. The catalytic deactivation was
retarded until 60 h over the former, in contrast to the
rapid deactivation over the latter, indicating that the initial
1905
J. S. Lee et al.
Figure 12. Test of catalytic deactivation over the Ni4Zr6/MCM-48 catalyst.
catalyst deactivation may have resulted from a combina-
tion of steam-induced nickel sintering and carbon deposi-
tion. However, the apparent deactivation rate was far
lower for the Zr-promoted catalyst, and its higher ethanol
conversion was maintained for up to 60 h. After 60 h, the
used catalyst was very black and was very dense. Thus,
the improved stability at the slower deactivation rate
achieved with the NiZr sample could not be unequivocally
attributed to carbon formation, as shown in Figure 11.
4. CONCLUSIONS
The two key study findings are the effects of the Zr addi-
tive in the Ni-loaded MCM-48 catalyst on the variation
in H2 production and the retardation of the catalytic deacti-
vation. On the basis of the performance results and a vari-
ety of physical measurements, we proposed that both the
Ni and Zr components played a role in the oxidation of
the feed gases during ethanol reforming. The simultaneous
addition of Ni and Zr may have depressed the sintering
between the Ni particles, and retarded the catalytic deacti-
vation. Consequently, their synergistic effect increased the
ethanol conversion and H2 production over the Ni4Zr6/
MCM-48 catalysts to 95% and 85%, respectively, over
a period up to 60 h. The optimum operation conditions,
as identified by a parametric study, were a reaction temper-
ature of 750
C, GHSV of 4000 h1, and feed ratio of
ethanol: H2O of 1:1.
ACKNOWLEDGEMENT
This work was supported by The New and Renewable En-
ergy of the Korea Institute of Energy Technology Evalua-
tion and Planning (KETEP) grant funded by the Korea
Ministry of Knowledge Economy (No. 2010T100100622).
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Hydrogen-rich gas production from ethanol steam reforming
REFERENCES
1. Rossia CCRS, Alonso CG, Antunes OAC, Guirardello R,
Cardozo-Filho L. Thermodynamic analysis of steam
reforming of ethanol and glycerine for hydrogen produc-
tion. International Journal of Hydrogen Energy 2009;
34:323–332.
2. Kim SC, Chun YN. Experimental study on partial
oxidation of methane to produce hydrogen using
low-temperature plasma in AC Glidarc discharge.
International Journal of Energy Research 2008;
32:1185–1193.
3. Youn MH, Seo JG, Jung JC, Park SU, Song IK.
Hydrogen production by auto-thermal reforming of
ethanol over nickel catalyst supported on mesoporous
yttria-stabilized zirconia. International Journal of
Hydrogen Energy 2009; 24:5390–5397.
4. Yasyerli S, Filizgok S, Arbag H, Yasyerli N, Dogu G.
Ru incorporated Ni–MCM-41 mesoporous catalysts
for dry reforming of methane: Effects of Mg addition,
feed composition and temperature. International
Journal of Hydrogen Energy 2011; 36:4863–4874.
5. Sania M de L, Ivna O da C, Jacobs G, Burtron HD,
Lisiane VM, Fabio BN. Steam reforming, partial
oxidation, and oxidative steam reforming of ethanol
over Pt/CeZrO2 catalyst. Journal of Catalysis 2008;
257:356–368.
6. Chein RY, Chen YC, Lin YS, Chung JN. Hydrogen
production using integrated ethanol-steam eforming
reactor with various reformer designs or PEM fuel
cells. International Journal of Energy Research
2012; 36:466–476.
7. Thaicharoensutcharittham S, Meeyoo V, Kitiyanan B,
Rangsunvigit P, Rirksomboon T. Hydrogen production
Int. J. Energy Res. 2013; 37:1896–1907 © 2013 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Hydrogen-rich gas production from ethanol steam reforming
by steam reforming of acetic acid over Ni-based
catalysts. Catalysis Today 2011; 164:257–261.
8. Wang X, Pan X, Lin R, Kou Y, Zou W, Ma J-X. Steam
reforming of dimethyl ether over Cu–Ni/g-Al2O3 bi-
functional catalyst prepared by deposition–precipitation
method. International Journal of Hydrogen Energy
2010; 35:4060–4068.
9. Wang W, Wang Y, Liu Y. Production of hydrogen by
ethanol steam reforming over nickel–metal oxide cata-
lysts prepared via urea–nitrate combustion method. Inter-
national Journal of Energy Research 2011; 35:501–506.
10. Alberton Andre L, Souza Mariana MVM, Schmal M.
Carbon formation and its influence on ethanol steam
reforming over Ni/Al2O3. Catalysis Today 2007;
123:257–264.
11. Zhang L, Liu J, Li W, Guo C, Zhang J. Ethanol steam
reforming over Ni-Cu/Al2O3-MyOz (M = Si, La, Mg,
and Zn) catalysts. Journal of Natural Gas Chemistry
2009; 18:55–65.
12. Santucci A, Annesini MC, Borgognoni F, Marrelli L,
Rega M, Tosti S. Oxidative steam reforming of ethanol
over a Pt/Al2O3 catalysts in a Pd-based membrane
reactor. International Journal of Hydrogen Energy
2011; 36:1503–1511.
13. Eswaramoorthi I, Dalai AK. A comparative study on
the performance of mesoporous SBA-15 supported
Pd-Zn catalysts in partial oxidation and steam reforming
of methanol for hydrogen production. International
Journal of Hydrogen Energy 2009; 34:2580–2590.
14. Wang F, Cai W, Provendier H, Schuurman Y,
Descorme C, Mirodatos C, Shen W. Hydrogen produc-
tion from ethanol steam reforming over Ir/CeO2 catalysts:
Enhanced stability by PrOx promotion. International
Journal of Hydrogen Energy 2011; 36:13566–13574.
15. Guo Y, Ran R, Shao Z, Liu S. Effect of Ba
nonstoichiometry on the phase structure, sintering,
electrical conductivity and phase stability of
Int. J. Energy Res. 2013; 37:1896–1907 © 2013 John Wiley & Sons, Ltd.
DOI: 10.1002/er
J. S. Lee et al.
Ba1xCe0.4Zr0.4Y0.2O3-d. International Journal of
Hydrogen Energy 2011; 36:8450–8460.
16. Wang L, Shao Y, Zhang J, Anpo M. Synthesis of
MCM-48 mesoporous molecular sieve with thermal
and hydrothermal stability with the aid of promoter
anions. Microporous and Mesoporous Materials
2006; 95:17–25.
17. Kwak BS, Lee JS, Lee JS, Choi B-H, Ji MJ,
Kang M. Hydrogen-rich gas production from etha-
nol steam reforming over Ni/Ga/Mg/Zeolite Y cata-
lysts at mild temperature. Applied Energy 2011;
88:4366–4375.
18. Zhao Q, Zhou X, Ji M, Wu D, Jiang T, Yin H.
Synthesis of ordered cubic mesoporous ZrMCM-48
molecular sieve with aid of fluoride ions. Colloid
Surface A 2011; 384:513–518.
19. Jiang T, Wu D, Song J, Zhou X, Zhao Q, Ji M, Yin H.
Synthesis and characterization of mesoporous
ZrMCM-48 molecular sieves with good thermal and
hydrothermal stability. Power Technology 2011;
207:422–427.
20. Pirouzmand M, Amini M.M, Safari N. Immobilization
of iron tetrasulfophthalocyanine on functionalized
MCM-48 and MCM-41 mesoporous silicas: Catalysts
for oxidation of styrene. Journal of Colloid Interface
Science 2008; 319:199–205.
21. Gies H, Grabowski S, Bandyopadhyay M, Grünert W,
Tkachenko OP, Klementiev KV, Birkner A. Synthesis
and characterization of silica MCM-48 as carrier of
size-confined nanocrystalline metal oxides particles
inside the pore system. Microporous and Mesoporous
Materials 2003; 60:31–42.
22. Jankhah S, Abatzoglou N, Gitzhofer F, Blanchard J,
Oudghiri-Hassani H. Catalytic properties of carbon
nano-filaments produced by iron-catalysed reforming
of ethanol. Chemical Engineering Journal 2008;
139:532–539.
1907