Fuel Processing Technology 149 (2016) 40–48

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Fuel Processing Technology

journal homepage: www.elsevier.com/locate/fuproc

Research paper

Ni/CeO2-thin ceramic layer depositions on ceramic monoliths for syngas

production by Oxy Steam Reforming of biogas
Riccardo Balzarotti a, Cristina Italiano b, Lidia Pino b, Cinzia Cristiani a, Antonio Vita b,⁎
a
Politecnico di Milano, Dipartimento di Chimica, Materiali e Ingegneria Chimica “G. Natta”, Piazza Leonardo da Vinci 32, 20133 Milano, Italy
b
Institute CNR-ITAE, Via Salita S. Lucia sopra Contesse n. 5, 98126 S. Lucia, Messina, Italy

a r t i c l e i n f o a b s t r a c t

Article history: Ni-CeO2 catalysts (metals load equal to 7.5 wt.%) as thin oxide layers on ceramic monoliths have been obtained by
Received 11 December 2015 support dip-coating into acid-free stable catalyst dispersion. Ni-based catalysts were prepared by precipitation-
Received in revised form 24 March 2016 dry-impregnation method or solution combustion synthesis and characterized by XRD, BET, CO-Chemisorption,
Accepted 2 April 2016
TPR, TEM and SEM-EDX techniques.
Available online 16 April 2016
Coating load (15–20 wt.%) was controlled by multiple depositions on the basis of the slurry rheological behavior.
Keywords:
Procedure goodness was evaluated in terms of coating load and adhesion performance. Homogeneous and well
Monoliths adherent layers of ca. 10–20 μm were found. The performance of final structured systems was evaluated towards
Washcoating biogas oxy-steam reforming (OSR) reaction, highlighting the influence of morphological and structural properties
Catalyst deposition of synthesized Ni-based powders on the catalytic activity. Catalytic tests demonstrated superior performances of
Nickel-ceria solution combustion synthesized Ni/CeO2 catalyst washcoated on monolith, especially at high space velocity.
Oxy-steam reforming © 2016 Elsevier B.V. All rights reserved.
Biogas

1. Introduction and a wider choice of materials, coupled with the possibility to regulate
the H2/CO molar ratio by changing the inlet gas composition [13,14].
Hydrogen is expected to be one of the main clean energy carrier in Ni-based systems have been widely investigated by many re-
the 21st century [1–3]. At present, the commercial production of hydro- searchers, showing good catalytic performances towards the reforming
gen is mostly based on steam reforming of fossil fuels, primarily natural processes [15–19]. Nevertheless, catalytic activities gradually decrease
gas [4,5]. However, from the standpoint of fossil fuels limitations and as a result of carbon deposition and sintering of active metals. A key
global climate changes, alternative ways are under investigation in issue for successful application of Ni-based catalysts consists in the solv-
order to replace fossil hydrocarbons with renewable sources. In this con- ing the deactivation phenomenon [15,20]. Redox support materials,
test, biogas represents a clean and environment friendly fuel that is typ- such as ceria-based solid solutions, or mixed oxides have been reported
ically generated from anaerobic degradation of biomass [6–8]. Moreover, to prevent metal sintering, due to strong metal-support interactions
hydrogen production from biogas is expected to promote the recycling (SMSI). Moreover, they are generally employed to mitigate catalyst de-
process in society [5,9,10]. activation by carbon deposition, due to oxygen storage capabilities
Among the various biogas reforming options, the Oxy Steam [21–23]. In addition, the adopted preparation method affects the mor-
Reforming (OSR) process, which consists in a combination of Dry phology of synthesized catalysts (namely crystallinity, homogeneity
Reforming (DR), Steam Reforming (SR) and Partial Oxidation (CPO) of and particle size), determining, in turn, catalytic activity and stability
methane in a single step, appears to be a valuable route [11,12]. The towards reforming processes [2,24].
presence of steam promotes SR and water gas shift (WGS) reactions, Structured catalysts and reactors for process intensification have re-
limiting the problem of carbon deposition which occurs in DR reaction. ceived large interest due to their peculiar characteristics, including high
Besides, the addition of O2 compensates the endothermic reforming re- geometric surface area and small pressure drop [5,25]. Structured sys-
actions, reducing significantly energy requirements by the endothermic tems with active components supported on different configurations
process (DR and SR) [2,12]. Moreover, OSR process offers several advan- (foams, honeycombs, gauze, microchannels) demonstrated many ad-
tages compared to other reforming alternatives: small unit size, lower vantages, providing an efficient heat and mass transfer compared to
energy requirements, lower operational temperature, easier start-up, conventional packed bed reactors [26]. In particular, monoliths have
been proposed for hydrogen production processes from biogas [25,27,
28]. One of the most critical issues for the fabrication of structured cat-
⁎ Corresponding author. alytic beds is the deposition of suitable active layers on the carrier, capa-
E-mail address: antonio.vita@itae.cnr.it (A. Vita). ble to withstand critical reaction conditions (oxidative environment,

http://dx.doi.org/10.1016/j.fuproc.2016.04.002
0378-3820/© 2016 Elsevier B.V. All rights reserved.
 R. Balzarotti et al. / Fuel Processing Technology 149 (2016) 40–48 41

Fig. 1. Catalyst powder XRD analysis: precipitation/dry impregnation (a) and solution combustion synthesis (b).

high temperature) and, in some cases, mechanical vibrations. Among novel organic bases solution, which was obtained by mixing water,
different deposition methods, dip-coating into a solution or a dispersion glycerol and polyvinyl alcohol. The latter formulation was used as
is widely considered the best procedure in order to washcoat geometri- alternative dispersion medium with respect to the commonly
cal supports [29–33], constituting the best compromise among costs, used acidic solutions. Ni/CeO2 catalysts were prepared using two differ-
time and efficiency [34]. ent preparation methods (i.e. the two-steps precipitation-dry-
The dip-coating process is based on the immersion of the morpho- impregnation method and the single-step combustion synthesis) and
logical substrate into a liquid phase, which contains the catalytic active characterized by XRD, BET, CO-Chemisorption, TPR, TEM and SEM tech-
phase precursor. Once substrates void are filled, the withdrawing pro- niques. Washcoating quality was evaluated in terms of coating load and
cess allows to create an homogeneous film on support surface, thanks adhesion performance. Therefore, the performance of the final struc-
to the balance between the gravitational force, which attract the film tured systems was evaluated towards the biogas oxy-steam reforming
downward, and the viscous force which hinders its sliding [35,36]. (OSR) reaction.
On these basis, rheological behavior and withdrawal speed are the
most important parameters in order to properly control coating layer 2. Experimental
formation [37]. Slurry rheological behavior depends on a large variety
of variables, both from the formulation components (binder, dispersant, 2.1. Catalyst preparation
solvent) and powder properties (properly sized powder, nature of
suspended solids) points of view. All those parameters directly influ- Catalyst powders were produced according to two different prepara-
ence viscosity, which is strictly connected to washcoat load/thickness tion routes, namely the combined precipitation-dry-impregnation pro-
and adhesion properties. As a matter of fact, low viscosity slurries cess and the solution combustion synthesis. In both cases a Ni content of
usually lead to low loads and high adhesion, while high viscosity formu- 7.5 wt.% was fixed. Ni content in the catalytic powder was confirmed by
lations promote high washcoat load but poor adhesion [36,37]. Disper- chemical analysis (ICP/OES).
sion stabilization and rheological properties are the major concerns in
slurry coating. Usually, acidic solutions are used in order to obtain stable 2.1.1. Precipitation-dry-impregnation
dispersions. Powder surface is covered by H+ ions and, thus, stability is It is a double steps process where the support is first obtained via
achieved by surface charging [37]. Unfortunately, this method is not ef- precipitation reaction and then it is impregnated by incipient wetness
fective both in case of low surface area and chemically inert powders. technique with a precursor of Ni active phase. A conventional precipita-
Moreover, some active phases or supports may be altered in case of tion procedure was applied to obtain the Ce-based support [40]. Accord-
acidic solution [38]. For these reasons, organic compounds have been ingly, Ce(NO3)3·6H2O (Sigma-Aldrich) was dissolved in water (1 M)
investigated as alternative dispersants [39]. and CeO2 was precipitated by adding a (NH4)2CO3 (Sigma-Aldrich)
In this work, new Ni-based structured catalysts were prepared for water solution (2.6 M) under magnetic stirring at room temperature.
the production of syngas by reforming processes. Ceramic monoliths The obtained slurry was filtered and the solid was washed until neutral
were used as structured supports (500 cpsi, diameter 1 cm, length pH. The resulting solid (reported as Ce-HS) was dried at 120 °C over-
1.5 cm), in which Ni/CeO2 (metals load equal to 7.5 wt.%) catalyst was night and finally calcinated at 500 °C for 3 h (2 °C min−1 of heating
deposited by support dip-coating into acid-free stable catalyst disper- rate). Incipient wetness technique [41] was applied to obtain the final
sion. Powder dispersion stabilization was achieved by means of a Ni-based catalyst (reported as NiCe-HS). Ni(NO3)2·6H2O (Sigma-
Aldrich) was used as precursor for the metal active phase. The impreg-
Table 1 nated powder was dried overnight at 120 °C and subsequently it
Main textural and structural properties of synthesized catalysts. was fired at 500 °C for 10 h (2 °C min−1 of heating rate). All the heat
treatments were carried out in air.
Sample BET X-ray Metal Ni
Surface dispersionb Particle
CeO2 CeO2 lattice NiO
area (%) sizec 2.1.2. Solution combustion synthesis
sizea parametera sizea
(m2/g) (nm) In a typical experiment, stoichiometric amount of Ni precursor
(nm) (Å) (nm)
(Ni(NO3)2·6H2O from Sigma Aldrich) and Ce precursor (Ce(NO3)3·6H2O
Ce-HS 90 4.8 5.410 – – –
from Alfa Aesar) were dissolved in the minimum quantity of distilled
NiCe-HS 80 5.5 5.409 15.2 1.0 30–60
Ce-UREA 14 11.4 5.394 – – – water (~100 ml) with the suitable quantity of fuel (CH4N2O, urea from
NiCe-UREA 10 11.3 5.380 – 2.2 3–5 Sigma Aldrich) [24]. The amount of fuel was determined by the so-
a
Calculated from X-ray diffraction: CeO2 crystallite size from Scherrer's equation of called fuel-to-oxidant ratio and calculated using the total oxidizing
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
CeO2 (111) reflection; Lattice parameter (α) from relation α ¼
2 2 2
h  k  l  ðλ=2  sinθÞ.
(O) and reducing (F) valencies of the components in order to have an
b
Determined by CO-pulse chemisorption. equivalence ratio equal to one (ф = O:F = 1), corresponding to a maxi-
c
Determined by TEM analysis. mum release of energy. The obtained solution was introduced into a
42 R. Balzarotti et al. / Fuel Processing Technology 149 (2016) 40–48

Fig. 2. TEM images of NiCe-UREA (a) and NiCe-HS (b) catalysts.

muffle furnace preheated at 350 °C and equipped with a thermocouple Before measurements all catalyst samples were reduced under pure
for the continuous monitoring of the temperature. In the beginning the H2 flow (30 Nml min−1) for 30 min at 500 °C.
solution boils, foams and then it undergoes intense flaming combustion On the same apparatus, catalysts reducibility was studied by H2
with evolution of gases (N2, CO2 and H2O), yielding a very voluminous temperature-programmed reduction (H2-TPR). A continuous flow of
powder. The resulting powders were calcined in air at 500 °C for 2 h 5% H2/Ar (30 Nml min−1) was passed over the catalyst and temperature
(5 °C min−1 of heating rate) to eliminate carbon residues of combustion. was raised up to 1000 °C with a rate of 20 °C·min−1. Before measure-
The obtained samples will be identified as Ce-UREA and NiCe-UREA. ments, all catalyst samples were treated in situ at 600 °C for 30 min
under O2 flow. H2 consumption was monitored by a thermal conductiv-
2.2. Catalyst characterization ity detector (TCD) and response was quantitatively calibrated from the
TPR area of known amounts of CuO.
Specific surface area was estimated from adsorption/desorption iso- SEM-EDX investigation of structured catalysts was obtained using a
therms at liquid nitrogen temperature (−196 °C) on Micromeritics ASAP FEI XL 30 microscope equipped with a field emission gun. TEM images
2020 instrument and calculated according to the Brunauer-Emmet- were obtained using a Philips CM12 microscope.
Teller (BET) equation.
X-ray diffraction (XRD) analysis of synthesized catalysts was 2.3. Washcoating
conducted by using a Philips X-Pert 3710 diffractometer equipped with
a Cu Ka radiation at 40 kV and 20 mA. X-ray diffraction patterns were Both catalytic materials (NiCe-HS and NiCe-UREA) were washcoated
recorded in the scan ranges of 2θ = 20°–75° (1.50° min−1) and 2θ = on cordierite monoliths (500 cpsi, diameter 1 cm, length 1.5 cm) sup-
27°–30° (0.06° min− 1) and 2θ = 42°–45° (0.06° min− 1). Crystallite plied by Applied Ceramics Inc. (USA). Powders slurries were obtained
size was calculated using Scherrer equation, from most intense reflec- according to literature [37]. Glycerol (87% w/w water solution, Sigma-
tion observed for NiO (200) and CeO2 (111) crystallographic structures, Aldrich) was used as dispersant and distilled water was used as solvent.
respectively. CeO2 lattice parameter (α) was obtained from the related A glycerol/powder ratio of 1.9 and water/powder ratio of 1.5 were
pattern at low scan rate. used, respectively. 2 wt.% of polyvinyl alcohol (PVA) (Mowiol from
Nickel dispersion was measured by CO-pulse chemisorption at room Sigma-Aldrich) related to water-glycerol mixture was used as rheology
temperature using a Micromeritics ChemiSorb 2750 instruments, modifier. In a typical experiment, the dispersion medium (HPG)
equipped with a TCD detector. A mixture of 10% CO in He was injected was produced by dissolving PVA in distilled water and then adding
in pulses of 600 Nμl each, until the fulfillment of constant outlet peaks. glycerol under magnetic stirring at 85 °C. Catalyst powder was thus
added to this solution and the resulting slurry was ball-milled using
ZrO2 spheres as grinding bodies for 24 h at 50 rpm in a polyethylene
jar. At the end of milling process, slurry was sonicated for 30 min
in order to reduce foaming. A dynamic stress device (Rheometrics)
was used to assess slurry rheological properties. Parallel disc plates
(diameter 40 mm) were used in order to investigate dynamic viscosities
in a shear rate range of 1–103 s−1. Temperature was controlled and it
was set at 25 °C. Before deposition process, structured supports were
washed in acetone by ultrasound bath for 30 min. Slurry deposition
was carried out by dip-coating, at constant withdrawal rate of
13 cm·min−1 for both dipping and withdrawal steps. Multiple dippings
were performed in order to obtain a coating load of 15–20 wt.%. After
each dipping, samples were flash dried in air for 6 min at 350 °C in
a sealed oven. In order to obtain the final coated catalysts, a 10 h
calcination process was performed at 800 °C (2 °C min− 1 heating
rate) [40].
Gravimetric analysis was performed after each flash drying
step and after the final firing process, in order to control weight
evolution and to assess washcoat load. Final washcoat load was deter-
mined by weight as the difference between the bare and the coated
support.
Coating adhesion was determined by sonication for 30 min in petro-
Fig. 3. H2-TPR patterns of NiCe-UREA and NiCe-HS catalysts. leum ether bath, according to literature [42].
 R. Balzarotti et al. / Fuel Processing Technology 149 (2016) 40–48 43

Fig. 4. Catalyst slurry rheological curves: precipitation/dry impregnation (a) and solution combustion synthesis (b).

2.4. Catalyst testing 3. Results and discussion

Biogas oxy-steam reforming (OSR) experiments were carried out in 3.1. Catalysts characterization
a quartz fixed-bed reactor (i.d. = 1 cm) inserted into a furnace
equipped with a PID temperature controller. Prior to reaction, struc- XRD patterns of synthesized NiCe-UREA and NiCe-HS catalysts are
tured catalysts were reduced by using 50% H2/N2 stream (30 Nml/ shown in Fig. 1 and they are compared with those of CeO2 carrier pre-
min) at 500 °C for 1 h. Then, catalytic performance was studied feeding pared by the same routes (Ce-UREA and Ce-HS). All systems showed a
a mixture of methane, carbon dioxide, oxygen and steam (in a molar typical cubic fluorite structure of ceria, corresponding to the (111),
ratio of CH4:CO2:H2O:O2:N2 = 1.0:0.67:0.3:0.1:0.1). High purity gases (200), (220), (311), (222) and (400) planes (reference JCPDS 4-593).
(99.999%, from RIVOIRA) were used in the experiments, keeping con- Particularly, the broadening of the diffraction peaks obtained for the
stant flow rates by means of mass flow-controllers (Brooks Instrument powders synthesized by precipitation-dry impregnation (HS) suggested
Smart Mass Flow). Steam was fed using an isocratic pump (Agilent the formation of materials with a major nanocrystalline component.
1100 Series) and a specially designed evaporator. Tests were carried Average crystallite size, which was calculated by Scherrer equation
out at a fixed temperature (800 °C); space velocity was varied and reported in Table 1, indicated for these systems crystallites smaller
(WSV = 35.000–250,000 Nml g−1 cat h
−1
) by changing flow rate from (ca. 5 nm) that those obtained for the UREA-samples (ca. 11 nm). Ac-
100 to 400 Nml min− 1 and by halving the monolith to reaches the cordingly, very different BET surface areas were measured for the sam-
highest WSV. Reaction temperature was measured at the centre of the ples, i.e. 80–90 m2 g−1 and 10–14 m2 g−1 for HS- and UREA-synthesized
catalyst bed by using a chromel/alumel thermocouple. In order to mea- samples, respectively.
sure the gradient temperature that was generated by reactions, two In addition, the preparation method also influenced the NiO crystal-
thermocouples were positioned at the inlet (TIN) and at the outlet lite size. Results evidenced NiO crystallite size of ca. 15 nm for NiCe-HS
(TOUT) of the catalytic bed respectively. The duration of each test was sample, while barely observable peaks were evident in the NiCe-UREA
set to 6 h. Reagents and products composition was determined catalyst. In the latter system, the peak shift to higher angles (Fig. 1)
using an on-line gas chromatograph (Agilent 6890 Plus) equipped with and the lattice contraction (5.380 Å compared to 5.394 of Ce-UREA) in-
thermal conductivity (TCD) and flame ionization (FID) detectors. On dicated the partial incorporation of smaller Ni2+ ions (rNi2+ = 0.81 Å)
TCD line, separation of O2, N2, CO, CO2, CH4, H2 and H2O was done into the lattice of ceria Ce4+ (rCe4+ = 0.97 Å) to form a Ce-Ni solid solu-
using argon as the carrier on a multicolumn system constituted by tion [43]. Therefore, a higher Ni-Ce interaction was noticed, while very
HP-PLOT “Q” (30 m, 0.53 mm, 15 μm), HayeSep “Q” and Molecular Sieves similar lattice parameter (5.410 and 5.409 for Ce-HS and NiCe-HS, re-
“13×” columns. On FID line, hydrocarbons separation was done on HP- spectively) indicated a poor Ni-Ce interaction, resulting in the formation
PLOT “Al2O3” (50 m, 0.53 mm, 15 μm) and Carbowax columns, using of larger NiO clusters (Table 1).
helium as carrier. CH4, revealed in both detectors, was used as reference Nickel dispersion values were obtained by CO pulse chemisorption
compound, while N2 was used as internal standard for mass balance. experiments. As reported in Table 1, the combustion synthesized
In addition, material balance (C, O and H) was calculated for each system (NiCe-UREA) showed higher dispersion value (2.2%) than the
experiment. precipitated-impregnated catalyst (1.0%), in agreement with NiO crys-
tallite size obtained by XRD analysis.
TEM micrographs of the studied systems are displayed in Fig. 2.
NiCe-UREA catalyst (Fig. 2a) showed Ni particles ranging between 3
and 5 nm, while large metal particles (30–60 nm) were clearly obtained
for the NiCe-HS system (Fig. 2b).
Catalysts reducibility was investigated by H2 temperature-
Table 2 programmed reduction; the related profiles are presented in Fig. 3.
Viscosity resume for cerium and nickel-cerium based slurries. Four hydrogen consumption zones (α, β, γ and δ) were observed, as
Sample Shear rate at Shear rate at Slop in 10–100 s−1 s previously reported [2,24]. The low-temperature α zone (temperatures
10 s−1 100 s−1 hear rate range range between 90 and 300 °C with a maximum at ca. 268–273 °C) is as-
Ce-HS 0.054 0.040 −0.144 cribed to the reduction of bulk NiO particles, which don't have any inter-
Ce-UREA 0.065 0.035 −0.289 action with ceria [44]. Besides, the contribution of the reduction of
NiCe-HS 0.023 0.023 −0.018 adsorbed oxygen due to the formation of NiO solid solution into CeO2
NiCe-UREA 0.039 0.029 −0.159
can't be excluded [43,45,46]. In the middle-temperature zone, the β
44 R. Balzarotti et al. / Fuel Processing Technology 149 (2016) 40–48

Table 3
Geometric properties of bare monolith.

Support Channel Inner size dp Wall thickness t Bed density Bed porosity Open frontal area ɛ Geometric surface area GSA
(mm) (mm) (kg/m3) (%) (m2/m3)

Bare monolith 0.83 0.32 771 72.5 0.52 2529

Coated monolith 0.80 0.34 926 72.4 0.49 2462

peak at 366–380 °C can be correlated to the reduction of NiO interacting ε¼

dp
2
[49]. Geometric surface area (GSA) was calculated according
2
with (but not chemically bound to) the support, while the γ peak at ðdp þtÞ

433 °C (not evident in the sample NiCe-HS) can be associated to the for- to the relation proposed by Cybulski and Moulijn [50]. The calculated
mation of Ni-Ce solid solution [24,44,47] and to the reduction of CeO2 geometric properties of coated systems slightly vary compared to that
surface oxygen [43]. The δ high-temperature zone is ascribed to the re- of bare support (Table 3). Catalytic layer deposition results in a decrease
duction of CeO2 bulk oxygen [44,45]. The calculated total reducibility of of channel inner size from 0.83 to 0.80 mm, while wall thickness in-
the samples were comparable (25.2 and 26.4 NmlH2 g−1 creases from 0.32 to 0.34 mm. Consequently, GSA value decreases to
cat for UR and HS
routes, respectively), while a significant different behavior could be 2462 m2/m3, compared to that of the bare support (2529 m2/m3).
seen in middle-temperature zone. It is evident that NiCe-UREA sample Results in terms of washcoat load as a function of dipping number
showed a comparable contribution of β and γ peaks, while the peak as- are reported in Fig. 5a. A linear trend between coating load and dippings
sociated to Ni-Ce solid solution formation resulted almost absent in number was clearly manifest in both samples, especially at low dipping
NiCe-HS catalyst. These results confirmed the low Ni-Ce interaction number. From the observation of the load-dipping curve, also good
and the presence of large surface NiO cluster for NiCe-HS catalyst, as washcoat process reproducibility was detected: the same coating load
shown by XRD analysis. was deposited after each dipping step. This suggests that coating load
The four powders, Ce-UREA, Ce-HS, NiCe-UREA and NiCe-HS, were is much more influenced by viscosity while wetting properties of the
dispersed in the HGP dispersant liquid medium, according to the proce- surface exert second order effects. Therefore, the nature of the coated
dure reported in Section 2.3. The obtained slurries were characterized surface does not or poorly influences the coating process, suggesting
from the rheological point of view and the results are reported in that process can be applied at any surface with or without very small
Fig. 4. Some differences in rheological behavior were observed: al- surface modification. Final coating load can thus be managed with a
though both morphological supports display a shear thinning behavior, multiple-dipping process up to the final load that is required for the ap-
Ce-UREA sample showed a more marked thinning behavior, resulting in plication. In this case, final washcoat load of 15–20 wt.% was reached
higher viscosity values at low shear rates. For the sake of comparison, after 6–9 dipping steps, depending on the sample, or more precisely
viscosity values and curves slope at typical dip-coating shear rates are on the slurry rheological behavior.
reassumed in Table 2. Ni active phase introduction resulted in a marked Indeed, the higher coating load per step obtained in NiCe-HS than in
modification of the flow curve, determining a decrease of absolute vis- NiCe-UREA (Fig. 5a) cannot be associated with the absolute viscosity
cosity. Moreover, a tendency towards Newtonian behavior (Ce-UREA) value; as a matter of fact, NiCe-HS viscosity is lower than that of NiCe-
and a less marked shear-thinning behavior (NiCe-UREA) were found. UREA (e.g. 0.02 and 0.04 Pa s at 10 s− 1, respectively). At the same
The observed changes could be due to a reduction in liquid phase/pow- time, a remarkable difference in slurry rheological behavior can be
der surface interaction, with an increase in solid chemical inertness. highlighted: at the shear of interest (10 s−1), NiCe-UREA dispersion is
shear thinning while the NiCe-HS one is Newtonian. Therefore the
3.2. Slurry deposition two dispersions could experience a different response to shear effects
during dipping process, thus explaining the slightly difference in the
Slurries based on both catalytically active powders were deposited reported load trend.
onto monoliths according to procedure reported in Section 2.3. From results in Fig. 5b, it is evident that calcination process did not
The main geometrical characteristics of bare and coated supports are affect the washcoat load obtained upon flash drying of the wet layer.
listed in Table 3. Channel inner size (dp) and wall thickness (t) were The minor change detected is justified by the final decomposition of res-
microscopically determined by using 30 different supports [48]. Bed idues of the organic dispersant that was not completely burned out dur-
density was calculated by using bed weight and volume. Bed porosity ing flash drying process. Moreover, considering that slurry composition
was determined by helium pycnometry. Open frontal area (ɛ) was cal- is the same in NiCe-HS and NiCe-UREA, not only the same final load is
culated from channel inner size (dp) and wall thickness (t) by equation obtained, but also the same shrinkage was observed upon calcination.

Fig. 5. Washcoat load evolution (a) and consolidation (b).

 R. Balzarotti et al. / Fuel Processing Technology 149 (2016) 40–48 45

Fig. 6. Back scattering SEM analysis of NiCeHS (a, c) and NiCeUrea (b, d) opened monoliths at different magnifications.

Adhesion tests in ultrasounds bath pointed out a higher washcoat- 3.3. Activity tests
support interaction for NiCe-UREA monolith. Losses of ca. 11 wt.%
after sonication were found, which have to be compared with those of Structured catalysts performance was investigated towards biogas
ca. 23 wt.% measured for NiCe-HS system. These results are in line Oxy Steam Reforming (OSR) at constant reaction temperature
with those obtained for other geometrical supports and similar (TSET = 800 °C) and reactants molar ratios (O2/C = 0.1, S/C = 0.3).
washcoat compositions [25,30,31,42], thus they can be considered The effect of space velocity (WSV = 35.000 and 250,000 Nml g−1 cat h
−1
)
acceptable. In addition, it has to be considered that ultrasound tests 1) was addressed and the results are shown in Fig. 8 in terms of meth-
are particularly stronger if compared to the stresses experienced by ane (χCH4) and carbon dioxide (χCO2) conversion and H2/CO molar
washcoat inside a reactor [31,32]. ratio. Recorded temperatures at the inlet (TIN) and at the outlet (TOUT)
Washcoat homogeneity and morphology were evaluated by SEM of catalytic bed are also reported, together with the equilibrium values
measurements on monolith channels surface by fracture analysis at 800 and 900 °C. At the adopted experimental conditions (reactants
(Fig. 6). Images acquisitions performed in back scattering allowed to mixture poor in oxygen and steam), prevalence of methane dry
distinguish between the deposited active layer (lighter regions of the reforming respect to steam and partial/total oxidation of methane, can
channel) and the geometrical support (darker regions). In line with ad- be predicted. Indeed, it should be noted that the adopted conditions
hesion tests results, monolith surface coverage is quite homogeneous, were more stressful for the catalytic systems than those reported in sim-
particularly in case of NiCe-UREA sample, which is the sample with ilar work in literature. NiCe-UREA monolith (Fig. 8a) showed almost
the best adhesion properties. Only a few areas are affected by the pres- constant catalytic activity in all the investigated WSV range. The mea-
ence of a non-optimal coverage degree. However, this phenomenon sured TIN and TOUT were always higher than TSET (800 °C at the center
seems rather due to the stress exerted when cutting the sample before of catalytic bed). It is widely reported [51,52] that syngas production
analyzing them by SEM than a real effect of a poor adhesion of the coat- by reforming reactions in presence of oxygen proceeds by a two steps
ed layer. By means of fracture analysis, coating thickness was evaluated path: i) methane combustion that produces H2O and CO2, followed by
for both NiCe-HS and NiCe-UREA coated monoliths. Results between ii) methane reforming reactions (with H2O and CO2) that produce syn-
10 μm and 20 μm were found, as reported in Fig. 7. gas. In the first part of catalytic bed, exothermic reactions (partial/total

Fig. 7. SEM analysis of NiCeHS (a) and NiCeUrea (b) coating thickness.
46 R. Balzarotti et al. / Fuel Processing Technology 149 (2016) 40–48

Fig. 8. Biogas OSR activity results on NiCe-UREA (a) and NiCe-HS (b) monoliths (Temperature, 800 °C; CH4:CO2:H2O:O2:N2 = 1.0:0.67:0.3:0.1:0.1; WHSV, 35,000–250,000 Nml g−1
cat h
−1
).

oxidation) occur, together with the partial oxidation of nickel species from 1.37 to 1.27 (Fig. 8b). Moreover, TIN and TOUT temperatures were
(with high activity for combustion reaction) [53]. After total oxygen higher than the set temperature, but they were lower (especially
consumption, in the second part of the bed, endothermic reactions TOUT) than those measured in test with NiCe-UREA; this could be due
(dry and steam reforming) prevail. The good balance between to a lower catalytic activity and, therefore, to a lower contribution of
oxidation-reforming zones determines the reforming activity of the cat- the endothermic reforming reactions. In this case, a deficit of ca. 4–8%
alyst. The presence of oxidation zone is confirmed by the high temper- in the C-mass balance could denote carbon deposition on catalyst
ature recorded as TIN, while the high temperature recorded at the surface.
outlet of the catalytic bed (TOUT) is due to the heat provided by furnace The obtained results were comparable with those reported in litera-
for supporting endothermic steam and dry reforming reactions [14,24]. ture [11,24,53–56]. Table 4 shows the main activity results on Ni-based
Experimental results obtained with the NiCe-UREA monolith were catalysts for biogas reforming processes (steam, oxidative and oxy-
in line with equilibrium values (reported at 800 and 900 °C), leading steam reforming). However, it is not easy to do a comparison in terms
to CH4 and CO2 conversion of ca. 96–97% and 86–87%, respectively. of CH4 and CO2 conversion, because the catalytic performances result
CH4 and CO2 conversions light increase by increasing WSV from from the combination of several operative parameters, such as temper-
35,000 to 70,000 Nml g−1 cat h
−1
and then decrease at higher space veloc- ature and inlet gas composition (CH4/CO2, steam-to-carbon and
ity. This confirms that the promoting effect of combustion reaction oxygen-to-carbon molar ratios), as well as structural and morphological
occurs only at low space velocity, as previously reported by Tomishige properties of catalytic system. As expected, the use of structured system
et al. [52]. Moreover, the light decay in the catalytic performance by instead of packed bed reactors allows to obtain stable performances, in
increasing WSV over 70,000 Nml g−1 cat h
−1
is due to the prevalence of ox- term of CH4 (97%) and CO2 (87%) conversion, also operating at higher
idation zone than reforming reactions. H2O conversion (nonshown in space velocity (250,000 Nml g−1 cat h
−1
).
Fig. 8) was ca. 60–61%, in line with equilibrium values calculated at Fig. 9 show SEM images of used NiCe-UREA (Fig. 9a) and NiCe-HS
800 (60.6%) and 900 °C (63.5%). In addition, an almost constant H2/CO (Fig. 9b,c) monoliths. No carbon deposits were observed for the NiCe-
molar ratio (1.36–1.37) was recorded (Fig. 8a). Recorded inlet temper- UREA system obtained by the combustion method (Fig. 9a), while a con-
ature was only slightly higher than TOUT, probably due to the low oxy- siderable amount of carbon was found in the NiCe-HS catalyst prepared
gen concentration in reactants mixture. Thus, both TIN and TOUT could by the precipitation-dry impregnation route (Fig. 9b,c). Moreover, EDX
be affected by furnace temperature. In addition, at high space velocity analysis of center channel view (Fig. 9c) of the latter system indicated a
the oxidative front moves from the inlet towards the inside of catalytic loss of catalytic material from the monolithic support, as confirmed by
bed along reactor axial direction. For this reason, a not accurate temper- the lower washcoat-support interaction determined by adhesion tests.
ature reading as TIN can't be excluded. The material balance on each Morphological and structural properties of synthesized Ni/CeO2 cat-
element (C, O and H) was carried out for this catalyst and values of ca. alysts affect catalytic activity in the OSR reaction. Low Ni-Ce interaction
98–102% were determined for all investigated WSV range. and the presence of large surface Ni cluster for the NiCe-HS system
Contrarily, catalytic tests carried out on NiCe-HS monolith (Fig. 8b) imply a poor resistance to carbon formation and, consequently, a rapid
showed a rapid decrease of catalyst performances. CH4 conversion de- deactivation of the catalytic system. As previously reported in literature
creases from 96 to 85% with increasing space velocity from 35,000 to [57,58], Ni crystal size is a dominating parameter for controlling the car-
140,000 Nml g−1 cat h
−1
. Similar trends were observed for CO2 and H2O bon filament growth. Indeed, carbon formation increases by increasing
(not shown) conversions, which decrease from 86% to 77% and from Ni crystallite size, due to the structure-sensitive nature of methane de-
61% to 43%, respectively. In addition, H2/CO molar ratio decreases composition reaction [58]. On the other hand, the superior physical-

Table 4
Literature activity results on Ni-based catalysts for biogas reforming processes.

Catalyst CH4/CO2 S/C O2/C WSV T χCH4 χCO2 H2/CO Ref.

(Nml g−1
cat h
−1
) (°C) (%) (%)

13 wt.%Ni/Ce-Zr-Al2O3 1.5 1.0 0.25 140,000 800 99 34 1.5 [11]

7.5 wt.%Ni/CeO2 1.5 0.3 0.1 14,000 800 95 88 1.4 [24]
11.5 wt.%Ni/Al2O3 1.5 0.7 – 20,000 800 97 50 2.1 [53]
10 wt.%Ni/SBA-15 2.0 1.0 0.6 24,000 800 96 56 1.4 [54]
8 wt.%Ni/Al2O3 1.5 – – 120,000 800 70 90 0.7 [55]
21.8 wt.%Ni/Al2O3 1.5 – 0.17 64,500 750 75 85 – [56]
7.5 wt.%Ni/CeO2/monolith 1.5 0.3 0.1 250,000 800 97 87 1.4 This paper
 R. Balzarotti et al. / Fuel Processing Technology 149 (2016) 40–48 47

Fig. 9. SEM images of used monoliths: frontal channel view of NiCe-UREA (a) and NiCe-HS (b); SEM-EDX analysis of the center channel view of NiCe-HS (c).

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