i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 0 9 5 6 e2 0 9 6 9

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Hydrogen production by ethanol steam reforming:

A study of Co- and Ce-based catalysts over
FeCrAlloy monoliths

mez a,
Yelisbeth Escalante a,*, Agustı́n E. Galetti a, Manuel F. Go
Octavio J. Furlong , Marcelo S. Nazzarro , M. Noelia Barroso a,
b b

M. Cristina Abello a
a
Instituto de Investigaciones en Tecnologı́a Quı́mica, INTEQUI (UNSL-CONICET), Facultad de Quı́mica Bioquı́mica y
Farmacia, Almirante Brown 1455, 5700, San Luis, Argentina
b
Instituto de Fı́sica Aplicada, INFAP (UNSL-CONICET), Av. Ejercito de los Andes 950, San Luis, 5700, Argentina

highlights graphical abstract

A new two-step strategy for the

catalytic coating of metal mono-
liths is developed.

An adherent and homogeneous
coating of MgAl2O4 over FeCrAlloy
monoliths is obtained.

Co and Ce are homogeneously
distributed on FeCrAlloy mono-
liths covered with MgAl2O4.

Migration of FeCrAlloy elements
towards the catalytic surface is not
detected.

The Co and Ce structured catalysts
exhibit a good performance in the
ESR reaction.

article info abstract

Article history: Co- and Ce-based structured catalysts deposited on FeCrAlloy monoliths have been pre-
Received 12 March 2020 pared. A new two-step strategy for coating the monolith is used: (i) first, a MgAl2O4 spinel
Received in revised form layer is generated on the FeCrAlloy substrate, and (ii) then, Co and Ce are incorporated in
1 May 2020 two different molar ratios by the conventional wet impregnation method. The spinel layer
Accepted 20 May 2020 is formed from a solution of colloidal alumina and Mg(NO3)2, with an apparent viscosity of
Available online 21 June 2020 around 3300 mPa s. The results indicate that a homogeneous spinel coating with excellent
adherence is obtained after two immersions and a calcination at 700  C. Both structured
Keywords: catalysts are active in the steam reforming of ethanol at 650  C. The system with a Co/Ce
Structured catalysts molar ratio of 3.7 exhibits the best performance with a high stability. A complete ethanol
CoeCeO2eMgAl2O4 monoliths

* Corresponding author.
E-mail address: escalanteyc@gmail.com (Y. Escalante).
https://doi.org/10.1016/j.ijhydene.2020.05.188
0360-3199/© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 0 9 5 6 e2 0 9 6 9
Hydrogen conversion and a hydrogen selectivity of around 95% are obtained in two reaction cycles of
Ethanol steam reforming 36 h each with intermediate regeneration.
© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Introduction
Hydrogen gas is considered as one of the future fuels, and
could participate in reducing environmental emissions. Un-
like fossil fuels, the combustion of H2 occurs without emitting
any environmental pollutants, since its combustion produces
only water as product. Furthermore, H2 is abundantly avail-
able in the universe and has a high energy content per unit of
weight (i.e. 120.7 kJ/g) compared to other fuels [1,2]. As fuel, H2
is of great value when obtained from renewable sources, such
as bioethanol since they involve environmentally friendly
processes [3]. Ethanol has several advantages compared to
other sources, such as its obtaining from biomass fermenta-
tion [4,5] and its easy handling and transport; it is biode-
gradable and has low toxicity. In addition, the CO2 generated
during the reforming process is consumed through photo-
synthesis during the plant growth [1,6]. For these reasons, the
ethanol steam reforming reaction has become a particularly
important alternative method for hydrogen production in an
environmentally friendly manner. Other ethanol trans-
formation reactions, mainly dehydrogenation, dehydration,
decomposition, among others [6], could also occur under
reforming conditions, leading to undesired by-products such
as acetaldehyde, ethylene, methane, etc., which are respon-
sible for carbon formation and catalyst deactivation.
C2 H5 OHðgÞ þ 3H2 OðgÞ/2CO2 ðgÞ þ 6H2 ðgÞ DH 298K
1
¼ 173:3KJmol
Transition metals such as nickel [7e11] and cobalt [12e18]
have been proposed as catalysts for steam reforming re-
actions. They have received considerable attention, due to
their high activity and ability to break CeC bonds, and to their
low cost and high availability compared to noble metals
[19,20].
Fixed bed reactors are the most used in catalytic reactions
but have some limitations. For instance, the heat transfer in
catalyst particles is highly inefficient. These reactors could
also present diffusion limitations through the catalyst pores
and serious pressure drops. In the case of the highly endo-
thermic ethanol steam reforming (ESR) reaction, the heat
transfer to the reactive system is a limitation to be considered
[21,22]. Numerous strategies using structured catalysts rather
than packed particles, have been proposed with the aim of ESR
process intensification. The most studied structured systems
are ceramic foams and monoliths [23e27]. For example, open-
celled foams decrease the pressure drops and enhance gas/
solid transfer phenomena, due to their high porosity with
tortuous paths, high surface-to-volume ratios and appropriate
20957
thermal conductivity. Palma et al. [26] have reported the
behavior of ethanol steam reforming at low temperatures
using a bimetallic PteNi/CeO2eZrO2 catalyst over a ceramic
foam. These authors found that at 450  C, a space velocity of
50,000 h₋1 and a H2O/C2H5OH molar ratio of 6 in the feed,
minimized carbon deposits formation and reactor plugging.
The foams geometry substantially enhanced coke gasification
reactions, without significant changes in H2 selectivity, and
avoided the plugging phenomena. A RhSiCeO2 catalyst sup-
ported on ceramic monoliths was employed by Moraes et al.
[27]; this system showed high H2 selectivity and stability in the
ESR reaction. Operating at 800  C, a H2O/C2H5OH molar ratio of
3.5 and a space velocity around 34,000 h₋1, the only products
were H2, CO and CO2. After 96 h of reaction, the catalyst
remained stable and no carbon was observed; although, at a
lower temperature, they observed methane and the formation
of carbon deposits.
Metal monolith reactors have also been proposed due to
their higher mechanical resistance and thermal conductivity
[22,28,29]. The possibility of having thinner walls allows a
higher cell density and lower pressure drop [28]. They have
been successfully used for the reforming of methanol [30e32]
or methane [33,34]. Sadykov et al. [35] have prepared struc-
tured catalysts over FeCrAlloy monoliths based on fluorite-
and perovskite-type mixed oxides, promoted by precious
metals (Pt, Ru) and/or Ni; these composite systems were
tested in reforming reactions of liquid fuels including ethanol.
The results showed a high syngas yield in the ESR at 750  C,
(1)
and the reaction products observed were: H2, CO, CO2, CH4 and
C2H4.
Only a few works have reported the application of Ni/
MgAl2O4 as catalytic material on metal foams and monoliths
in reforming reactions [36e38]. Cristiani et al. [36] have re-
ported the preparation and performance of FeCralloy foams
for methane steam reforming (MSR) using Ni/MgAl2O4. The
catalytic foam proved to be highly active in the reaction, with
H2, CO and CO2 as main products. Recently, Katheria et al. [37]
studied the effects of different process variables on the
coating loading and adhesion of Ni/MgAl2O4 on FeCralloy
monoliths. They compared the performance of a catalytic
metal monolith with a conventional packed-bed reactor in the
MSR process. The coated monolith was found to be more
active in comparison with the packed-bed reactor, which was
attributed to the lower pressure drop and a decrease in heat
transfer limitations. The same authors studied the effect of Rh
doping on Ni/MgAl2O4 catalysts and its application on metal
monoliths [38]. They observed a significant increase of 24% in
methane conversion when Rh was incorporated into the Ni/
MgAl2O4 structured catalyst. As expected, the coated metal
20958 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 0 9 5 6 e2 0 9 6 9

monolith showed higher catalytic activity, hydrogen yield and

stability, in comparison with the packed-bed reactor.
An interesting alternative for the intensification of the
reforming process will be to combine the use of structured
catalysts with membrane reactors. This configuration could
be an alternative to be integrated with PEM fuel cells, where a
stream of high-purity H2 is required. Pd-based membrane re-
actors have shown high efficiency and selectivity in H2
permeation, [39e43]. Spallina et al. have studied Pd-based
membranes in a fluidized bed catalytic reactor and a Pt
(3 wt.%)- Ni(10 wt.%) catalyst deposited on a mixed CeO2/SiO2
support, and have reported a hydrogen recovery factor of up to
70% in the ethanol auto-thermal reforming reaction [40]. The
same idea could be developed and validated using structured
catalysts.
According to these results, it is interesting to expand these
studies using catalytic metal monoliths in the ESR reaction,
and to our best knowledge, CoeCeO2/MgAl2O4 as catalytic
material in structured system has not been investigated. In
the present work, the optimization of relevant parameters in
the deposition of CoeCeO2/MgAl2O4 catalytic material over
metal substrates of FeCrAlloy, and its catalytic performance in
the ESR reaction, is presented. Co, like Ni, is a good candidate Scheme 1 e Preparation of a structured catalyst by the
as active phase in the preparation of catalysts for reforming washcoating method.
alcohols, due to its previously mentioned characteristics.
Likewise, the addition of Ce into catalysts has improved their
stability and increased their deactivation resistance by carbon
temperatures generates oxide layers on the surface of the
deposition [44]. At the same time, MgAl2O4 as catalytic support
FeCrAlloy, which offer the necessary roughness to improve
contributes with its moderate basicity and high thermal sta-
adhesion between the metallic structure and the catalytic
bility. Monoliths were coated using the washcoating method,
material.
due its simplicity and versatility. The behavior of structured
catalysts in the ESR was compared with that of a packed-bed
Deposition of catalytic material
reactor containing a powder catalyst.
The deposition of catalytic material over the metallic struc-
ture was carried out by the washcoating method in two stages:

Material and methods

(i) Spinel generation (MgAl2O4), which acts as catalytic
support, by immersion of the pretreated monoliths in a
Sample preparation
gel containing the spinel precursors.
(ii) Incorporation of Co and Ce over coated monoliths by
Commercial FeCrAlloy monoliths provided by Shanghai Wis-
wet impregnation, from an aqueous solution with a Co/
dom Technologies (L ¼ 4 cm, Ø ¼ 2 cm and 400 cpsi) were used
Ce molar ratio of 2.4 or 3.7.
to obtain structured catalysts. The chemical composition in
the metal monoliths provided by the supplier was: 70 wt.% Fe;
Generation and deposition of the MgAl2O4 layer
22 wt.% Cr, 5 wt.% Al and traces of other elements such as Ti.
The pretreated structured substrates were coated with a
Foils of 1  1 cm obtained from monoliths were used to
spinel layer. A viscous solution was prepared from Mg(NO3)2-
facilitate the characterization of materials and determine the
$6H2O and a commercial colloidal suspension of alumina
efficiency of the preparation procedure.
(AL20, Nyacol Nano Technologies, Inc.) in a Al/Mg molar ratio
The experimental procedure for preparing structured cat-
of 2. The pretreated monoliths were dipped into the solution
alysts is illustrated in Scheme 1. First, the metal monoliths
for 1 min, followed by removal of the excess solution by
were cleaned followed by a thermal treatment at high tem-
blowing with compressed air (5 psi) for 1 min. The coating
perature. Then, the pretreated monoliths were dipped into a
process was repeated several times using the same solution
viscous solution containing the spinel precursors. Finally, the
with a drying step at 90  C in vacuum for 30 min, with or
metallic phases were incorporated over the coated monoliths
without an intermediate calcination at a given temperature
by wet impregnation.
for 2 h. The influence of the number of immersions, the effect
of drying or calcination between each immersion, and the
Surface pretreatment
intermediate calcination temperature were evaluated. Table 1
The metal monoliths were cleaned with acetone at room
summarizes the studied conditions. The monoliths (M) and
temperature under ultrasonic vibration for 30 min. Then, the
foils (F) were named as MxyT or FxyT, where x is the number
samples were treated at 900  C for 10 h at a heating rate of
of immersions, y refers to s: only intermediate drying between
10  C min₋1 [37]. According to the literature, pretreating at high
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 0 9 5 6 e2 0 9 6 9 20959

each immersion, or c: with intermediate calcination, and T ¼ Sample characterization

600 or 700  C. Thus, for example, M2c700 and F2c700 identify a
monolith and a foil with a layer of MgAl2O4, respectively, ob- Rheological properties
tained after 2 immersions, with intermediate calcination at The rheological behavior of the viscous solution was studied
700  C. The coating loading percentage (%WL) was calculated using a Brookfield viscometer, Model DV-111. The change in
by the following equation: viscosity as a function of the shear rate was determined, and
  the apparent viscosity value was found.
wf  wi
%WL ¼ x 100 (2)
wi
Adherence test
where wf and wi represent the weight of coated and uncoated The adherence of the coated monoliths was evaluated using a
monolith, respectively. Branson ultrasonic bath, model 1210, and the weight loss after
the test was recorded. The monoliths were immersed in
Incorporation of Co and Ce acetone and exposed to ultrasonic waves for 30 min at room
The metallic phases were incorporated by wet impregnation temperature. Then, they were dried at 90  C for 2 h. The
on the monoliths coated with MgAl2O4. Aqueous solutions of adhesion test results are presented as percentage of adher-
Co(NO3)2$6H2O and Ce(NO3)3$6H2O were prepared in distilled ence (A%), which was evaluated as
water with two Co/Ce molar ratios: 2.4 or 3.7. The monoliths  
W  Dw
(or foils) were immersed in the metal solutions for 1 min, A% ¼ x 100 (3)
W
followed by blowing with compressed air (5 psi) for 1 min.
Then, the samples were dried under vacuum at 90  C for 12 h, where W represents the weight of catalyst loaded over the
and calcined at 650  C for 3 h, obtaining the final structured monolith, and Dw is the difference between the monolith
catalyst. Immersions were repeated until obtaining the weight before and after the ultrasonic test.
desired metallic load. The loading of Co and Ce oxides was
recorded by mass difference between the monolith before Chemical composition
and after the immersions. Monoliths and foils containing Co The cobalt content in the impregnation solutions was deter-
and Ce were named as MCoCez or FCoCez, where z repre- mined by atomic adsorption using a Shimadzu atomic ab-
sents the Co/Ce molar ratio. Thus, MCoCe2.4 and FCoCe2.4, sorption spectrophotometer AA-6300. The elementary
correspond to a monolith and a foil, respectively, with a composition of FeCrAlloy was confirmed by inductively
MgAl2O4 layer impregnated with a Co/Ce molar ratio equal to coupled plasma-atomic emission spectroscopy (ICP-AES),
2.4. using a sequential ICP spectrometer Baird ICP 2070 (BEDFORD)
with a Czerny Turner monochromator (optical path of 1 m).
Powder-supported catalyst For this analysis, a FeCrAlloy foil with dimensions of
For comparative purposes, a powder-supported catalyst was 0.5  0.5 cm was disintegrated in a mixture of concentrated
prepared by the co-impregnation of Co and Ce on the MgAl2O4 acids (3 mL HNO3 and 1 mL HCl).
support. The support was obtained from the same viscous
solution, prepared as indicated in section Deposition of Scanning electron microscopy and energy dispersive X-ray
catalytic material (i), dried under vacuum at 90  C for 12 h, spectroscopy
and calcined at 700  C for 3 h. After impregnation, the solid The homogeneity and uniformity of the material incorporated
was dried under vacuum at 90  C for 12 h and calcined at onto the metal substrates were examined by scanning elec-
650  C for 3 h. The catalyst was denoted as CoCe3.7, where the tron microscopy (SEM). The elemental chemical composition
value 3.7 represents the Co/Ce molar ratio. The nominal was identified with an analyzer (EDAX Genesis 2000) coupled
metallic loads of Co and Ce were of 12 and 8 wt.%, respectively. to the microscope.
This sample was characterized by the BET method, XRD and
TPR [17]. X-ray photoelectron spectroscopy
X-Ray photoelectron spectra were collected using a VG
Microtech ESCA spectrometer with a non-monochromatic Al
Ka radiation source (300 W, 15 kV, hn ¼ 1486.6 eV), combined
with a VG-100-AX hemispherical analyzer, operating at a pass
Table 1 e Number of immersions, calcination
energy of 25 eV. The instrument resolution was of 0.1 eV. All
temperature, loaded weight and adhesion test.
binding energies (BE) were referred to the adventitious C1s
Substrate ni Tcal, MgAl2O4 weight, % A
 peak at 284.8 eV, to correct spectral shifts due to charging
(monolith) C mg WL (%)
effects. The chamber pressure was kept at <109 Torr during
M1c600 1 600 52.0 0.18 100 the measurements.
M2c600 2 600 128.6 0.44 100
M1c700 1 700 52.0 0.18 100
M2c700 2 700 128.6 0.44 100
Optical images
M2s700 2 700 128.6 0.44 100 The coated monoliths were analyzed by optical microscopy.
M3s700 3 700 153.0 0.53 99 The images were acquired using an Olympus Nano-Scope
M4s700 4 700 184.3 0.63 99 OMV-PAL optic system, which captures images in digital
ni ¼ number of immersions. format. The ImageJ software was used to analyze all images.
20960 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 0 9 5 6 e2 0 9 6 9
X-ray diffraction
Diffraction patterns of powders (XRD) were obtained using a
RIGAKU diffractometer, model Ultima IV- type II, operated at
30 kV and 20 mA, using Cu Ka radiation (l ¼ 0.15418 nm). The
samples were analyzed with a scanning rate of 3 min1 in the
2q range from 10 to 90 . The crystalline phases were identified
by matching with the JCPDS files.
Temperature programmed reduction measurements
Temperature programmed reduction (TPR) measurements
were performed in conventional TPR equipment [10]. Before
the experiment, the sample was subjected to an oxidizing
atmosphere under a mixture of O2 (13%)/He flow (50 mL min1)
at 300  C for 1 h, and then to a He flow (30 mL min1) for
30 min. Then, the sample was cooled down to room temper-
ature in a helium atmosphere. Subsequently, the sample was
reduced in a H2 (5 vol%)/N2 flow (50 mL min1) from room
temperature to 900  C, at 10  C min1, and kept at that tem-
perature for 1 h. The H2 consumption was determined after a
previous calibration.
Catalytic test
Ethanol steam reforming was carried out at 650  C and at-
mospheric pressure. A tubular metal reactor with the same
diameter as the metal monoliths (40 mm) was employed. The
reaction temperature was controlled by a thermocouple inside
of the monolith central channel. The feed stream was a liquid
mixture of water and ethanol (H2O:C2H5OH ¼ 4.9:1), which was
taken to an evaporator (operated at 130  C) at 0.15 mL min1 or
0.20 mL min1 through an isocratic pump. Two different inlet
ethanol concentrations were used, 9.4 or 12.5 M%. The W/
FC2H5OH was calculated excluding the monolithic substrate
weight. Before reaction, the catalysts were reduced in situ
with a H2 (5%)/N2 flow at 650  C for 1 h. For the powder cata-
lyst, a fixed-bed quartz tubular reactor with 4 mm in internal
diameter was used and loaded with 50 mg of catalyst without
dilution. The reactants and reaction products were analyzed
on-line using two gas chromatographs. H2, CH4, CO2 and H2O
were resolved by a 1.8 m Carbosphere (80e100 mesh) column
and analyzed by a TC detector. Nitrogen was used as an in-
ternal standard. CO, after passing through a methanizer, was
also analyzed by a flame ionization detector (FID). C2H4O,
C2H4, C3H6O and C2H5OH were separated in a Rt-U PLOT
capillary column and also analyzed by a FID using N2 as a
carrier gas. The ethanol conversion (XC2H5OH), selectivity to
carbon products (Si) and hydrogen yield (YH2) were defined as
C2H5OH  FC2H5OH
Fin out
XC2H5OH ¼ *100
Fin
C2H5OH
ni Fout
Si ¼  i *100
C2H5OH  FC2H5OH
2 Fin out
Fout
YH2 ¼ in
H2
FC2H5OH
Fin out
i and Fi are the molar flow rates of product “i” at the inlet
and outlet of the reactor, respectively, and ni is the number of
carbon atoms in “i”.
The H2 selectivity was calculated considering that 6 mol of
H2 represents 100% of selectivity (Eq. (1)).
Results and discussion
Treatment of FeCrAlloy structured substrates and foils
The surface treatment of monoliths is of great importance
since it plays a key role in the adhesion and durability of
structured catalysts. Alloys containing aluminum, such as
FeCrAlloy, have the advantage that Al diffuses to the surface
during thermal treatment, forming oxide layers of Al2O3
[45,46]. These oxide layers are responsible for improving the
adherence and/or chemical compatibility between metal
substrate and catalytic material [28,37,47]. In this work, after
the treatment with acetone (section Surface pretreatment),
foils and structured substrates of FeCrAlloy were thermally
treated at 900  C for 10 h. SEM-EDX images of the foils are
shown in Fig. 1. For comparison, a FeCrAlloy foil without
treatment was also examined. As can be observed from
Fig. 1A, the untreated FeCrAlloy foil presents a smooth surface
with some irregularities. EDX analysis shows the presence of
Fe, Cr, Al and Ti as minor component, in agreement with the
supplier’s information. At the same, this information was
confirmed by ICP, which showed the following elementary
composition: 72.3 wt.% Fe, 19.3 wt.% Cr, 7.4 wt.% Al and
1.0 wt.% Ti.
After thermal treatment, the formation of a rough layer
enriched with Al and O is clearly observed by EDX, which al-
lows to infer that an oxide layer was formed (Fig. 1B). Similar
results on thermal pretreatment have been reported [46]. The
samples were calcined for 10 h, and agglomerates of particles
with enough roughness were observed, instead of the whisker
type structures typically showed in substrates treated at high
temperature for more than 12 h [30,31]. Although the thick-
ness of the alumina layer was not measured, some authors
have reported that it is around 3 mm for monoliths treated at
900  C for 22 h [31].
Preparation of a viscous solution of MgAl2O4
In the literature, structured catalysts are usually prepared
from a stable slurry containing the catalyst particles. The
particle size, pH and viscosity of the solution are critical pa-
rameters to be controlled during the preparation procedure.
The solution viscosity is strongly influenced by the solid
content in the slurry. An optimal viscosity in the range be-
(4) tween 5 and 30 mPa s has been proposed by several authors
[48,49]. The particle size should be in the colloidal range (about
2 mm), which also implies a controlled milling process. In this
work, a new strategy was employed. The structured catalyst
(5)
was prepared in two steps: (i) first, a spinel layer was gener-
ated on the treated FeCrAlloy substrate, and (ii) then Co and Ce
were incorporated by the conventional wet impregnation
(6) method as indicated in the experimental section.
A viscous solution was prepared from Mg(NO3)2$6H2O and
a commercial colloidal suspension of alumina. The resulting
solution presented a viscosity value outside the mentioned
range, since it is a viscous solution obtained from the spinel
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 0 9 5 6 e2 0 9 6 9 20961

Fig. 1 e SEM Images with EDX of FeCrAlloy foils: (A) untreated, (B) treated at 900  C, (C) two immersions and calcination at
600  C (F2c600), (D) two immersions and calcination at 700  C, (F2c700), (E) two and (F) three immersions, with intermediate
drying and calcination at 700  C (F2s700 and F3s700, respectively).

precursors and not from the dispersion of catalytic solid par-
ticles in a viscous medium. This solution was characterized to
determine its rheological properties. Fig. 2 shows the variation
of solution viscosity with shear rate. A decrease in viscosity
with increasing shear rate is observed, corresponding to a
non-Newtonian shear-thinning type of behavior [37,50]. In
addition, a hysteresis loop is revealed when the shear rate
increases from zero to a maximum value, and then decreases
back to zero. This behavior is characteristic of time-dependent
fluids [51]. The larger the area enclosed, stronger will be the
time-dependent behavior. Therefore, it can be inferred that
the solution (hereafter called “slurry”) is a time-dependent
non-Newtonian fluid with an apparent viscosity of around
3300 mPa s. It is well known that low viscosities require a
greater number of immersions to achieve high loads [47]. This
slurry, as will be seen later, allows the deposition of attractive
amounts of the spinel from a low number of immersions, due
to its high viscosity.
Washcoating of FeCrAlloy monoliths and foils
A series of monoliths and foils were coated using the wash-
coating method. As mentioned above, the number of immer-
sions, drying with or without intermediate calcination and
calcination temperature were some of the evaluated param-
eters. These parameters and the coating loading percentage
(WL%) are compiled in Table 1. As expected, the amount of
MgAl2O4 loaded over the metal monoliths, as well as the
20962 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 0 9 5 6 e2 0 9 6 9
Fig. 2 e Variation of solution viscosity with respect to the
shear rate.
values of WL%, increased with the number of immersions.
Thus, two immersions result in a load of approximately
129 mg of spinel support.
All monoliths with a MgAl2O4 layer presented an excellent
adherence in the ultrasound test, even those with more than 3
immersions, Table 1. These results indicate that there is a
good chemical compatibility between spinel and treated sub-
strates. In contrast, the calcination temperature has an in-
fluence on the homogeneity and surface composition of the
coated material.
Presented in Fig. 1C and 1D are the SEM micrographs of two
foils, F2c600 and F2c700 (calcined at 600 and 700  C, respec-
tively). The foils calcined at 600  C showed an inhomogeneous
surface, with the presence of agglomerated particles enriched
with Mg and O, which could suggest the formation of MgO.
This phase was not observed in the diffraction pattern (not
shown) of a spinel in powder (calcined at 600  C), possibly due
to that the size of the MgO crystallites is below the detection
limit of the technique. On the other hand, the foils calcined at
700  C showed a homogeneous surface, suggesting a greater
uniformity in the coating. The analysis by EDX reflected the
elements of the spinel (Al, Mg and O) and those corresponding
to the FeCrAlloy. From these results, it could be inferred that
the appropriate calcination temperature for a MgAl2O4 ho-
mogeneous coating over metal substrates is 700  C.
As mentioned above, the treatment between each im-
mersion was evaluated. In Fig. 1D and 1E, SEM micrographs for
two foils coated with two immersions, one dried with an in-
termediate calcination (F2c700), and the other dried without
such calcination (F2s700) are presented, respectively.
Regardless of the treatment between immersions, both foils
were finally calcined at 700  C. A uniform and homogeneous
coating is observed in both foils, which indicates that the in-
termediate calcination of the foils does not affect the final
appearance of the coating. Despite the excellent adherence in
monoliths with three or more immersions, the SEM analysis
reveals the appearance of some cracks on the surface (Fig. 1F).
The presence of these cracks can compromise the useful life
of the structured catalyst since the catalytic material could
break off under reaction conditions. According to the results,
structured catalysts were prepared from monoliths coated
with two immersions without calcination between immer-
sions, and then finally calcined at 700  C (M2s700) to ensure a
uniform and homogeneous coating.
The surface of the F2s700 foil (which is representative of
M2s700) was analyzed by XPS in order to determine the sur-
face chemical composition of the coated substrates. The XPS
spectra exhibited peaks at binding energies corresponding to
Mg2p (49.9 eV), Al2p (74.3 eV) and O1s (530.7 eV), Fig. 4 [52]. The
presence of Fe, Cr or Ti was not detected. This result reflects
that there is no migration of FeCrAlloy matrix elements to-
wards the surface of the coated foil.
Incorporation of Co and Ce
The coated monoliths and foils were immersed in the solution
containing the Co and Ce metallic salts. The Co composition of
each impregnation solution was verified by atomic adsorp-
tion. The content of Co in the solution with a Co/Ce molar ratio
of 2.4 was of 12373.5 ppm (nominal value: 14084.3 ppm),
whereas it was of 21854.0 ppm (nominal value: 23695.2 ppm)
for the one with a Co/Ce molar ratio of 3.7. The experimental
concentrations of Co were less than the nominal, since the
cobalt nitrate used to prepare the solutions is not a standard
reference material.
Presented in Fig. 5A is a SEM micrograph of a foil containing
the catalytic material CoeCeO2/MgAl2O4 (FCoCe2.4), with its
corresponding elemental mapping. The elemental mapping
shows the distribution of elements on the FeCrAlloy matrix.
Co and Ce are homogeneously distributed on the metal sub-
strate. This result suggests that the method used to incorpo-
rate the metal phases over the coated monoliths is highly
efficient to obtain disperse particles. The FCoCe3.7 foil was
also analyzed by SEM, Fig. 5B, and the elemental distribution
of Co and Ce was also homogeneous. In agreement with the
preparation conditions, the Co content was higher than in the
FCoCe2.4 foil.
Foils containing the catalytic material were also analyzed
by XPS. The elements present on the substrate surface, the
oxidation state of Co and Ce species, and the Co/Ce surface
molar ratio were determined. No treatment was performed
before the XPS experiments, and the results are summarized
in Table 2. The XPS spectrum of Co2p3/2 exhibited peaks with
typical binding energies of Co2þ and Co3þ, assigned to the
Co3O4 oxide, Fig. 6A. The XPS spectrum of Ce3d5/2 shown in
Fig. 6B reveals peaks at binding energies corresponding to
Ce3þ (n , n0 ) and Ce4þ (n, n00 , n000 ) [53].
In addition, the spinel elements were also observed, unlike
those in the FeCrAlloy matrix. The surface Co/Ce molar ratios
reflect the molar ratios used in the preparation (the Co/Ce
given by XPS were of 2.5 and 4.5 against the nominal Co/
Ce ¼ 2.4 and 3.7, respectively), which suggest a high dispersion
of the metallic species.
Some characteristics of the structured catalysts are sum-
marized in Table 3. The weight of catalytic material on the
substrate varied between 162 and 185 mg. The Co/Ce molar
ratios given by XPS and SEM-EDX are close to the nominal
values.
Optical images of the catalyst loaded on the monolith walls
are shown in Fig. 3D and 3E. They reveal that the incorporation
of metal phases seems to be homogeneous with no evidence
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 0 9 5 6 e2 0 9 6 9 20963

Fig. 3 e Optical images of FeCrAlloy monoliths: (A) untreated, (B) two immersions (M2s700), (C) four immersions (MF4s700),
(D) MCoCe2.4, (E) MCoCe3.7, (F) MCoCe2.4 after 36 h of reaction, (G) MCoCe3.7 after 36 h of reaction (Feed liquid
flow ¼ 0.20 mL min¡1) and (H) MCoCe3.7 after the second reaction cycle (Feed liquid flow ¼ 0.15 mL min¡1).

Fig. 4 e X-ray photoelectron spectra of a coated foil (F2s700) showing the Al2p, Mg2p and O1s regions.

of blocking the monolith structure channels. It is well known
that the stability and durability of a coated material over a
metal substrate depends largely on its chemical compatibility
and adhesion strength [47]. The MCoCe2.4 and MCoCe3.7
monoliths exhibited excellent adherence, Table 3. Therefore,
it can be inferred that the structured catalysts prepared would
remain stable and durable during the catalytic tests.
Characteristics of CoCe3.7 powder catalyst
highest temperature (maximum temperature 835  C) could be
assigned to the reduction of Co species that are strongly
interacting with the support [17], and probably to the reduc-
tion of the bulk CeO2 [20]. The H2/Co molar ratio determined
from the total H2 consumption in the TPR profile was of 0.97,
and clearly indicates that the Co species are not completely
reduced until 900  C (the theoretical value of the H2/Co molar
ratio for complete reduction of Co species is 1.33, assuming
the following reaction Co3O4 þ 4H2/ 3 Co þ 4H2O)

Table 4 summarizes some characteristics of the powder
catalyst. MgAl2O4 (JCPDS-21-1152), Co3O4 (JCPDS-42-1467) and
CeO2 (JCPDS-34-0394) were detected by XRD (not shown).
Three reduction peaks were observed by TPR (not shown).
The peaks located at 361  C and 473  C can be attributed to the
reduction of Co3þ/Co2þ (Co3O4) species interacting with CeO2
and/or interacting weakly with the support [20,54,55]. The
hydrogen consumption at low temperature range also corre-
sponds to the surface reduction of CeO2 [20]. The peak at the
Catalytic study in ethanol steam reforming reaction
The ethanol steam reforming reaction was studied over the
coated monoliths at 650  C. In Fig. 7A and 7B, the catalytic
behavior of both monoliths with a W/FC2H5OH of 2.82 g h mol₋1
based on the catalyst weight on the monolith walls is shown.
The total catalyst mass on the structured system with a Co/Ce
molar ratio equal to 2.4 was of 169 mg, Table 3. Based on the
oxides weight, the estimated metal load is around 7 wt.% for
20964 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 0 9 5 6 e2 0 9 6 9

Fig. 5 e SEM micrograph (upper-left) and elemental mapping of foils containing the catalytic material CoeCeO2/MgAl2O4. (A)
FCoCe2.4 and (B) FCoCe3.7.

Table 2 e XPS results for foils containing the CoeCeO2/MgAl2O4 catalytic material.
Binding energy, eV Surface ratio
Foil Co2p3/2 Ce3d5/2 Co2þ/Co3þ Ce3þ/Ce4þ Co/Ce
2þ 3þ  0 00 000
Co Co n n n n n
FCoCe2.4 780.9 779.0 880.6 885.0 882.0 888.0 897.5 0.52 0.44 2.54
FCoCe3.7 780.9 778.9 880.5 884.9 882.1 888.1 897.1 0.36 0.59 4.52

each metal. For Co/Ce ¼ 3.7, the total catalyst mass was of
176.5 mg, and the estimated metal load is around 10.6 Co wt.%
and 7 Ce wt.%. Both structured catalysts were active in the
reforming reaction but showed differences in the products
selectivity. The main products detected were hydrogen, car-
bon dioxide, carbon monoxide and methane. Acetaldehyde
and traces of ethylene and acetone were only detected for the
structured catalyst with the lowest Co/Ce molar ratio. A stable
and high H2 yield was detected for the highest Co/Ce molar
ratio, around 5.7 mol H2/mol C2H5OH (selectivity to H2 95%),
whereas it was an average of 4.9 mol H2/mol C2H5OH for the
Co/Ce molar ratio of 2.4. The results suggest that the increase
in Co content improves H2 production, while decreasing the
amount of minority products.
In the literature, the steam reforming of ethanol over
ceramic structured catalysts has been studied. Moraes et al.
[27] have reported a good performance in ESR on Rh/SiCeO2
supported on a ceramic monolith at 800  C. Lopez et al. have
also informed a H2 yield of 3.4 mol H2/mol C2H5OH at 677  C
and 1.5 bar over a Rh (0.5 wt.%)- Pd (0.5 wt.%)/CeO2 catalyst
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 0 9 5 6 e2 0 9 6 9 20965

-based foams with a silicon carbide carrier [26]. They showed

Fig. 6 e X-ray photoelectron spectra of the FCoCe2.37 foil.
(A) Co2p region (shows the peaks of Co2p3/2 for Co3þ and
Co2þ) and (B) Ce3d region (shows the peaks assigned to
Ce4þ and Ce3þ).
deposited on a cordierite monolith. Although the catalytic
performance was kept constant for uninterrupted 75 h on
stream, the authors claimed that a deactivation process was
observed [56]. Palma et al. have also studied the catalytic
behavior and deactivation resistance of NiePt/CeO2eZrO2
that the binder used in the preparation plays an important
role in preventing deactivation. A fast deactivation of the
catalytic foam containing SiO2 as binder was observed. They
considered that, under reforming conditions, the steam can
attack the Si atoms of the silica structure, opening the SieOe
Si bond and re-bonding the two silanols. Consequently, Ni
and/or Pt particles can be wrapped and/or buried into the
silica and the system losses activity. However, the choice of
boehmite as binder substantially improved the catalyst sta-
bility, allowing the coke gasification reactions. In the present
work, the structured catalyst with a Co/Ce molar ratio of 3.7
showed a good performance in ESR at 650  C without the use
of noble metals in the catalyst composition. In addition, the
catalytic coating preparation method used is simple, repro-
ducible and without the binder addition.
The structured catalysts showed high stability, which
could be attributed to improvements in heat and mass
transfers [30,37]. After 36 h under reaction conditions, the
structured catalysts were removed from the reactor and
weighted. The weight gains shown in Table 5 were attributed
to carbon deposits.
The influence of the inlet ethanol concentration was also
studied on MCoCe3.7. The inlet ethanol concentration was
increased to 12.5% (Flow: 0.20 mL min₋1 instead of
0.15 mL min1 at the same H2O/C2H5OH molar ratio). The
catalytic results shown in Fig. 7C are similar, with a complete
ethanol conversion and high stability during 36 h. The H2 yield
was lower (5.5 mol H2/mol C2H5OH) due to an increase in CH4
selectivity (5.8%). The carbon accumulation rate was of 1.5
10₋2 mg C min₋1, Table 5.
The optical images of catalytic monoliths after reaction
shown in Fig. 3F and 3G revealed the formation of carbon
deposits, although no channel blockage was evidenced. The
carbon deposits were lower when the Co/Ce molar ratio
increased, in agreement with the results shown in Table 5.

Table 3 e Some characteristics of the structured catalysts.

Structured catalysta Catalyst load, mg wt.% Nominal ratio Co/Ce Co/Ce molar ratiob A(%)
Co Ce XPS SEM-EDX
MCoCe2.4 169.0 7.3 7.3 2.4 2.5 2.5 nd
162.8 6.1 6.1 99
MCoCe3.7 176.5 10.6 7.1 3.7 4.5 3.4 nd
190.5 10.8 7.2 98
185.3 10.7 7.2 nd

nd: not determined.

a
Prepared from M2s700 monolith.
b
Determined from FCoCe2.4 and FCoCe3.7 foils.

Table 4 e Composition and properties of the powder-supported catalyst.

Sample Co/Ce nominal ratio SBET, m2/g XRD phases Tpeak, C H2/Co molar ratio
I II III
CoCe3.7 3.7 76 Co3O4, CeO2 and MgAl2O4 361 473 835 0.97

Surface area of spinel support: 145 m2/g, Phase observed by XRD: MgAl2O4.
20966 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 0 9 5 6 e2 0 9 6 9

Fig. 7 e Distribution of products and conversion in the ethanol steam reforming reaction over (A) MCoCe2.4 (Feed liquid flow
0.15 mL min¡1, W/FC2H5OH ¼ 2.82 g h mol¡1), (B) MCoCe3.7 (Feed liquid flow 0.15 mL min¡1, W/FC2H5OH ¼ 2.82 g h mol¡1), (C)
MCoCe3.7 (Feed liquid flow 0.20 mL min¡1, W/FC2H5OH ¼ 2.3 g h mol¡1) and (D) CoCe3.7 (Feed liquid flow 0.15 mL min¡1, W/
FC2H5OH ¼ 0.8 g h mol¡1). Reaction temperature: 650  C, H2O:C2H5OH molar ratio ¼ 4.9:1.

For comparison, the behavior over the CoCe3.7 powder respectively, with traces of C2H4 (0.7%). The W/FC2H5OH was
catalyst under similar reforming conditions is presented in lower for the powder catalyst in comparison with the mono-
Fig. 7D. The catalyst weight was of 50 mg, without any diluent liths. The selectivities towards these products remained
in order to observe possible catalyst deactivation in a short almost unchanged during 480 min of reaction. The presence of
reaction time. At the beginning, the powder catalyst exhibited carbon deposits affecting the catalyst stability was corrobo-
a 98% of conversion, decreasing near to 10% after 3 h of re- rated by TG-TPO analysis (not shown). The observed weight
action, and then this value remained constant. The H2 yield loss between 360 and 560  C was of 23%, and it is attributed to
was around 4.7 mol H2/mol C2H5OH. The main carbon prod- the combustion of deposited carbon, Table 5. The maximum
ucts were CO2 and CO, with a CO2/CO molar ratio of around 1. combustion temperature is lower than that found over other
The selectivities to CH4 and C2H4O were of 5 and 8%, Co catalysts [17,18], probably due to differences in CoeCeO2
interactions. The formation of filaments was evidenced by
SEM (not shown). Co and Ce signals were also observed in the
Table 5 e Formation of carbon during the ethanol steam EDX spectrum, indicating that the metallic particles have not
reforming on CoeCe catalysts. been yet encapsulated by carbon. The lower W/FC2H5OH for the
powder catalyst compared to the monoliths, justifies the dif-
Catalyst Reaction %C Carbon accumulation rate,
time, min mg C min1 ferences in the products distribution, but the greater amount
of carbon deposits associated with the activity loss leads to
MCoCe2.4 2133 26.2 0.020c
presume a greater instability of this system.
MCoCe3.7 2138 22.3 0.018c
MCoCe3.7a 2139 14.6 0.012c
MCoCe3.7b 2108 17.4 0.015c Regeneration
CoCe3.7 480 23.1 0.024d
a
After the second reaction cycle over regenerated catalyst. Since the best performance was observed for the structured
b
Feed liquid flow: 0.20 mL min₋1. catalyst with the Co/Ce molar ratio of 3.7, this system was
c
Determined from the difference between monolith weight before regenerated after 36 h in reaction by heating in an oxygen
and after the catalytic test. stream diluted in nitrogen, 94 mL min₋1 of 6% O2/N2. The
d
Determined by TG-TPO for used powder catalyst. temperature was varied from 150  C to 650  C at 10  C min₋1,
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 0 9 5 6 e2 0 9 6 9
Fig. 8 e Catalytic behavior of the MCoCe3.7 structured
catalyst during two cycles with an intermediate
regeneration. Reaction temperature: 650  C, H2O:C2H5OH
molar ratio ¼ 4.9:1, inlet liquid flow: 0.15 mL min¡1,
ethanol concentration: 9.4%, W/FC2H5OH ¼ 2.82 g h mol¡1.
and maintained at 650  C for 40 min. Then, the amount of
oxygen was increased to 21% for another 20 min, to ensure the
removal of deposited carbonaceous species. The COx evolu-
tion was followed by GC, and the regeneration was stopped
when the COx production decreased practically to zero. Then,
the system was cooled in a He flow. The regenerated monolith
was removed from the reactor and weighted (171.0 mg). It
could be inferred that the initial weight was recovered. After
that, a new catalytic cycle with a previous reduction (in a H2
(5%)/N2 flow at 650  C for 1 h) was carried out, and the results
are shown in Fig. 8. The catalyst recovered the activity and the
products distribution. An excellent response in this reaction
cycle was observed. Again, the monolith was removed and
weighted. The carbon accumulation rate was of 1.2 10₋2 mg C
min₋1, Table 5. In the literature, few works have been reported
about regeneration procedures [27]. The optical image after
the second reaction cycle is shown in Fig. 3H.
Conclusions
The deposition of CoeCeO2/MgAl2O4 on FeCrAlloy monoliths
was successfully achieved with excellent adherence and a
good homogeneity of the catalytic coating. The results indi-
cated that a highly viscous solution obtained from Nyacol and
magnesium nitrate allowed to obtain highly adherent and
homogeneous coatings of magnesium spinel, which was used
as support to incorporate the active phases. According to the
XPS analysis, no migrations of the FeCrAlloy matrix elements
towards the surface of the spinel were observed after two
immersions with intermediate drying and a final calcination
at 700  C. The incorporation of Co and Ce on the monoliths
covered with the spinel, in two different molar ratios, was also
carried out successfully. A high adherence of the catalytic
material was observed. The absence of Fe or Cr from the
20967
FeCrAlloy matrix on the surface, and a high dispersion of Co
and Ce, were revealed by XPS.
Both structured catalysts were active in the ethanol steam
reforming reaction at 650  C and atmospheric pressure. The
system with Co/Ce molar ratio of 3.7 exhibited the best per-
formance with a high stability. The hydrogen selectivity was
around 95% with complete ethanol conversion during two
reaction cycles of 36 h each. The activity and selectivity to
hydrogen after regeneration between cycles were recovered,
showing an excellent response. From this result, it could be
inferred that the regeneration procedure was suitable.
Acknowledgments
This work was supported by CONICET (PIP 00327), National
University of San Luis (Project PROICO 2-0116), and the ANP-
CyT (PICT 1470-2014). The authors wish to thank Dr. Cristian
Illanes (INFAP) for Optical Microscopy assistance.
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