Catalysis Today xxx (xxxx) xxx

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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

H2 production by methane steam reforming over Rh/Al2O3 catalyst packed

in Cu foams: A strategy for the kinetic investigation in
concentrated conditions
Matteo Ambrosetti 1, Danilo Bonincontro 1, Riccardo Balzarotti , Alessandra Beretta ,
Gianpiero Groppi , Enrico Tronconi *
Politecnico di Milano, Dipartimento di Energia, Via Lambruschini 4, 20156, Milano, Italy

A R T I C L E I N F O A B S T R A C T

Keywords: The concept of Rh/Al2O3 catalyst pellets packed in highly conductive copper foams has been successfully tested
Methane steam reforming kinetics in methane steam reforming showing the beneficial effects of thermal conductivity on the obtainment of
Hydrogen gradient-less radial temperature profiles. In this work, the same concept is proposed as a strategy for the lab-scale
Rhodium catalyst
kinetic investigation under concentrated conditions at ambient pressure; thanks to the homogeneous heating of
Process intensification
Open-cell foams
the catalyst mass across the reactor section and the measurement of axial temperature profiles, well-controlled
temperature conditions are obtained, and the experimental investigation can be extended to usually unfeasible
conditions of high reactant concentrations, overcoming the typical challenges for the kinetic study. Here, steam
reforming experiments were performed with CH4 and H2O feed molar fractions in the ranges of 10− 20 % and
40–90 %, respectively. The co-feed of CO and H2 was also investigated. A kinetic scheme was developed that
substantially confirmed the main results of previous kinetic investigations in annular micro-reactor, performed
under diluted conditions; in particular, the first order dependence of the rate of steam reforming on methane
partial pressure, the independence from H2O partial pressure, and the important inhibiting effect of CO were
confirmed. The independence of the reaction rate from the H2 co-feed was here demonstrated for the first time.
The new experimental campaign allowed to identify more clearly the kinetic dependencies of the water gas shift
reaction, positively influenced by H2O partial pressure but scarcely affected by CO partial pressure, which could
be also explained based on the inhibiting effect of surface CO coverage. Parameter estimates were obtained by
model fit over a wide temperature range (400− 850 ◦ C), conveying robustness to the proposed kinetic scheme for
future reactor design applications.

1. Introduction MSR CH4 + H2 O →CO + 3 H2 ΔH (298 K) = +206 kJ/mol (1)

In the history of Industrial Chemistry, Hydrogen has represented one WGS CO + H2 O →CO2 + H2 ΔH (298 K) = − 41.1 kJ/mol (2)
of the most important chemicals. According to International Energy The endothermic character of the MSR reaction calls for efficient
Agency [1], chemical and petrochemical applications account for more heat supply at high reaction temperatures, which is obtained by the
than 95 % of pure hydrogen and 70 % of the total hydrogen demand, the multi-tubular design of the reformer, where slender catalyst-packed
majority of which is used for ammonia production, methanol production tubes are externally heated by burners and flue gases. To promote the
and refining processes. These are characterized by an economy of scale radial heat transfer in the tubes (the limiting step of the process), high
and therefore require large and centralized H2 plants [2,3]. flow velocities are required, and 10− 12 m long tubes are needed to
Methane Steam Reforming (MSR) is the most used H2 production reach almost complete CH4 conversion [3]. The reactor is operated at
technology. The process involves both methane reforming with steam high pressures, as required by the end-users. Industrial catalysts for
and water gas shift: methane steam reforming are typically based on Ni/MgAl2O4

* Corresponding author.
E-mail address: enrico.tronconi@polimi.it (E. Tronconi).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.cattod.2021.06.003
Received 5 March 2021; Received in revised form 25 May 2021; Accepted 3 June 2021
Available online 6 June 2021
0920-5861/© 2021 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

Please cite this article as: Matteo Ambrosetti, Catalysis Today, https://doi.org/10.1016/j.cattod.2021.06.003
M. Ambrosetti et al. Catalysis Today xxx (xxxx) xxx

formulations that provide an optimal tradeoff between cost, activity and found proportional to the partial pressure of CH4 and independent from
long term stability under the severe operating conditions [4–6]. the concentration of H2O and reaction products, an indication of the
Optimized at the large scale, the MSR technology is little flexible to unique kinetic relevance of the first C–H bond cleavage. Water gas shift
scaling down. However, the growing penetration of low-carbon was found to be fully equilibrated. Due to the high level of bed dilution,
hydrogen uses as clean energy vector calls for the development of a the experiments could be reliably evaluated only within the differential
distributed network of H2 production. New hydrogen applications conversion regime, which is an important limitation in the perspective
include transportation, industrial and residential heating and Combined of reactor design applications.
Heat and Power (CHP) generation [7,8]. In the transition to a fully green Integral data were instead collected in our laboratory by using an
and decarbonized H2-production capacity, small-scale fuel processors annular reactor, especially designed for running kinetic tests of fast
can represent the key for supporting in the short term the H2 demand of catalytic reactions, at high space velocity and under controlled tem­
the energy market. Despite decades of experience in the design of perature conditions [27,28]. The reactor consists of an annular duct,
large-scale steam reforming units, two main factors challenge the which is obtained by introducing a catalyst coated ceramic capillary into
intensification of MSR: (i) the high endothermicity of the reaction and a quartz tube; because of a very efficient heat radiation mechanism from
(ii) the need of suitable catalysts able to grant high yields of H2 also at the catalyst surface, partial oxidation, steam reforming and CO2-r­
intermediate temperatures. eforming experiments could be performed under quasi-isothermal con­
In order to mitigate problems associated to heat transfer at the small ditions. In fact, the axial temperature profile was characterized by very
scale, several kinds of structured reactors have been proposed for the limited gradients (few degrees over the catalyst layer length) under
intensification of energy-demanding catalytic processes [9]. One of the diluted conditions (1–4 % v/v CH4 concentration). By means of reactor
possible approaches is the coupling at the micro-scale of endothermic modelling (including the impact of inter-phase mass transfer limita­
and exothermic reactions with coated micro-channel reactors to pro­ tions), the kinetics of methane, CO and H2 fuel rich oxidations, as well as
mote the heat exchange between the two processes [10–12]. The the kinetics of methane steam reforming and water gas shift over
application of conductive internals has been proposed as a solution to Rh/Al2O3 were obtained. Similarly to Iglesia and coworkers’ studies
reduce the thermal gradients inside the reactors and improve the process [25,29], the rate of steam reforming was found proportional to the
productivity; in early studies, stainless steel structures were proposed in methane concentration and unaffected by H2O concentration; however,
steam reforming applications thanks to their tolerance to high temper­ the data collected in integral regime evidenced an overall reaction order
atures [13–15]. However, the nature and geometry of the metal support lower than one, which ascribed to the inhibiting effect of products
and the resulting effective thermal conductivity need to be optimized for adsorption. Besides, water gas shift was non-equilibrated below 500 ◦ C.
the single process to obtain the desired beneficial effect. The heat Partial oxidation experiments were also performed under concentrated
transfer properties of different structured catalysts (i.e, open-cell foams, feed streams (27 % v/v CH4), at the expense of pronounced but
monoliths and more recently periodic open cellular structures – POCS) measurable axial temperature gradients. These concentrated tests were
have been investigated in our group [16–18] and showed the potential used to verify the adequacy of the C1 kinetic model. Additional pieces of
of these structures. Open-cell foams are interconnected solid structures evidence on the prevailing kinetic dependences and the evolution of
composed by a solid matrix characterized by ligaments that create surface coverages were provided by a micro-kinetic study, incorporating
interconnected cells communicating through windows. Thanks to this DFT estimates of the enegetics [30].
feature, open-cell foams enable high effective heat transfer properties The kinetic investigation has been extended to the partial oxidation
through the conduction in the solid metal. The small cell size enable high and steam reforming of several other hydrocarbon fuels [31,32];
surface area and increase the wall heat transfer coefficient [19].For the throughout the studies, the kinetics of the water gas shift has been
catalytic applications, both washcoating with thin active layers [12,20] further refined [22] with the proposal of a main kinetic dependence on
or packing with small catalytic pellets [21] were proposed as feasible H2O partial pressure. Notably, in all these experimental campaigns, the
strategies. In the case of methane steam reforming the use of Cu-foams total C concentration has been limited on purpose to 3% (molar) in order
either washcoated or packed with Rh/Al2O3 catalyst particles has to minimize temperature gradients along the axial coordinate and the
been proved to be highly promising for the process intensification [20, radial gradients across the gas and solid phases.
21]. In particular, in [21] the outstanding performances of packed To overcome such limitations, an entirely new strategy was needed.
copper open-cell foams were demonstrated. On one side, packing allows Thanks to the superior heat and mass transfer properties granted by the
for a reasonably high catalyst inventory if small pellets are adopted, on presence of the conductive reactor internals based on open-cell foams,
the other side remarkably high heat transfer properties are realized by the Rh/Al2O3 formulation was herein tested in methane steam reforming
the synergy between the packing and the conductive internals. Besides, under considerably larger concentration of reactants, while spanning
the use of a Rh based formulation guarantees high intrinsic activity in a throughout the entire integral regime from low to high conversions. The
wide temperature range and low coking tendency [22]. new experimental campaign has offered the opportunity to verify in a
In this work, the same reactor concept has been applied to a more more stringent way the kinetics of methane steam reforming and water
fundamental objective, that is the extension of the kinetic investigation gas shift previously proposed and thus develop a more robust kinetic
of methane steam reforming on Rh to concentrated H2O/CH4 feeds at model.
ambient pressure. As well known, the kinetic study of fast and highly
exothermic or endothermic reactions is challenged by irreducible mass 2. Materials and methods
and heat transport resistances [23]. Traditional packed-bed reactors
suffer from the onset of important radial and axial temperature profiles 2.1. Catalyst preparation and characterization
that hinder a rigorous kinetic investigation [24]. Use of fine particles,
dilution of the catalyst bed and/or of the reactant mixtures are common The catalyst used in this work is the same already used in previous
strategies of mitigation of the thermal and diffusional effects. Iglesia and investigations of the group [18,19]. Catalytic tests were performed using
co-workers obtained a gradient-less reactor configuration by intro­ a home-made Rh/Al2O3 catalyst in the form of egg-shell particles to
ducing a very large degree of dilution both at the scale of the particle and avoid the presence of internal mass transport limitations. Alumina
at the scale of the bed [25]; diluted feed streams were used as well. The particles (Puralox by Sasol, 600 μm nominal diameter, d50 = 660 μm)
“infinitely” diluted reactor design was applied to a very wide and sys­ were preliminary dried in a static oven at 120 ◦ C overnight; then, Rh was
tematic investigation of the kinetic regimes of CH4 activation with O2, deposited by wet impregnation by diluting Rh (NO3)3 liquid solution
H2O and CO2 over noble metal catalysts, including Rh, Pt and Pd [25, (12.5 %wt. metal content by Alfa Aesar) with deionized water. The
26]. In the case of Rh-catalyst, the rate of CH4 steam reforming was amount of solution was calculated with an excess of 25 % with respect to

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M. Ambrosetti et al. Catalysis Today xxx (xxxx) xxx

the pellet pore volume saturation, while the solution concentration was configuration as described in Balzarotti et al. [21] In particular, one of
calibrated to reach a Rh content per mass of pellet equal to 0.3 wt %. them was placed at the centerline of the foam (Center-T, figure), a
The catalytic material was characterized in a previous work [21] second one was placed at r = R/2 (Radial-T) and the third one was
with a scanning electron microscope (ZeissEvo50 EP) equipped with an placed outside the reactor (Wall-T), solidly soldered to the reactor wall.
energy dispersive X-ray spectrometer (EDX) to determine the concen­ In this way, it has been possible to measure the temperature profiles
tration profile of rhodium in the radial direction of cross-sectioned during the tests by sliding the thermocouples with a sampling resolution
catalytic pellets. in the axial direction equal to 5 mm, along 12.5 cm. As shown in Fig. 1c,
The total metal content, in terms of Rh◦ with respect to the Al2O3 axial coordinate has been defined in order to have the origin of this
matrix, was found to be equal to 0.28 %wt. with respect to Al2O3 support length 2.5 cm before the catalytic bed.
mass, which is in good accordance with the specification (0.3 %wt.) The As far as the operative conditions of the catalytic tests are concerned,
dispersion of Rh was previously quantified equal to 90 % by H2 the oven temperature has been modulated within the 400− 750 ◦ C range,
chemisorption. while three different Gas Hourly Space Velocities (GHSV) have been
The thickness of the egg-shell layer was found to be 38 ± 2 μm, which tested: 32900, 65700 and 98600 N L h− 1 kg−cat1. In terms of reaction
is consistent with results reported in literature for catalysts produced mixture compositions, different H2O/CH4 (S/C) ratios have been
with a similar preparation procedure [21,33]. A posteriori analysis of employed to investigate the effect of composition on the reaction ki­
internal mass transport limitations was performed with the kinetic netics. In particular, the first experiments have been carried out modi­
model derived from the experimental tests by calculating the local fying the CH4 and H2O molar fraction between 9.75–19.50 % and
effectiveness factor. 40.25–90.25 %, respectively, and using N2 as complement, corre­
sponding to a molar steam to carbon ratio (S/C) in the range 4.1 – 8.3. A
2.2. Experimental setup second group of tests aimed at evaluating the effect of products co-
feeding and was performed by introducing precise amount of CO and
Catalytic tests have been carried out in a lab scale reactor inserted in H2 to the feed.
a controlled temperature furnace (Carbolite GERO 30–3000 EVZ 1200, Catalytic tests at fixed operative conditions (GHSV = 65700 N L h− 1
-1
Fig. S2 e). The reactor is an AISI 310S stainless steel tube, 68 cm long and kgcat Toven = 500 ◦ C, S/C = 4.1 CH4 = 19.5 %) to evaluate catalyst sta­
with an internal diameter of 2.95 cm and external diameter of 34 mm. bility have been carried out after each experimental run.
Packed foam catalytic bed (7.5 cm) was prepared using as internals six
40 PPI (pores per inch) copper foams segments (ERG Duocell, cell 3. Results
diameter (dcell) =2 mm, void fraction εf = 0.89). The foams were kept in
the desired position (40 cm from the bottom of the reactor) by a spacer 3.1. Characterization of the thermal behavior of the system at varying
composed by a 40 PPI FeCrAl foam soldered with the two internal load: effects of heating temperature and total flow rate
thermowells (see Fig. S1 in SI). A FeCrAl felt was used to separate the
FeCrAl foam and the copper ones to retain catalytic bed particles. The Catalytic tests were carried out to fully characterize the thermal
latter were loaded as described in Balzarotti et al. [21] by gentle pouring performances of the system (i.e., axial and radial temperature profiles)
from the top in order to fill the foam cavities. In order to improve at varying heating temperature and integral CH4 conversion, that is at
packing efficiency, the reactor was gently shaken during the catalyst varying total thermal load; in practice, experiments were performed by
loading. This combination of pellet and foams allows a good packing, increasing the oven temperature from 450 to 700 ◦ C and the total flow
thus avoiding gas bypass and void regions in the catalytic bed as pre­ rate from 2 to 6 Nl/min. The experiments were performed at the con­
viously reported [34]. Thus, the foams have been filled with 3.93 g of stant S/C ratio of 4.1, in non-diluted conditions (CH4 feed molar fraction
Rh/Al2O3 pellets and 26.17 g of bare Al2O3 pellets, with a resulting void of 19.5 %). The results are reported in Fig. 2, in terms of measured
fraction of the packed foam (εPF = 1-Vpellet/(VF*εf)) of 0.48, in line with conversion vs heating temperature (panel a) and vs. a representative
previous results. A porosity lower than 0.55 can be considered as a safe reactor temperature (panel 2b), at three levels of space velocity.
value to exclude the presence of bypass in the reactor that may influence At the smallest GHSV of 32900 N L h− 1 kg−cat1 and increasing heating
catalytic measures [34]. On top of catalytic bed, 3 cm of inert Al2O3 temperature, the measured CH4 conversion grew from about 10 % to
pellets (dpellet =1.6 mm Puralox by Sasol) have been loaded to allow full about 95 %. At each heating temperature, then, lower conversions were
mixing of the reactants. progressively measured at increasing space velocity, a clear indication of
Reaction mixture has been fed downward from the reactor top. CH4, the kinetic sensitivity of the system (Fig. 2a). At the highest space ve­
CO, H2, N2 (SAPIO, purity 99.999 %) have been fed through separate locity of 98600 N L h− 1 kg−cat1, the measured conversion grew from 5 to 75
lines and their flow rates has been controlled by dedicated flowmeters % at increasing heating temperature. Thus, in the entire experimental
(Brooks SLA5800 Series, Figs. S2b in SI). Water vapor was fed to the campaign, the reactor experienced an overall change of the thermal load
reactor, first feeding a calibrated amount of liquid water (stored in two by a factor of over 20.
vessels, Figs. S2a in SI) through a flowmeter (Brooks IP40 QUANTIM In each experiment, the axial temperature profile at the three radial
Series, Figs. S2c, in SI) followed by an evaporator (Brooks VDM300, coordinates was measured, thus monitoring the whole temperature
Figs. S2d in SI). All the lines between evaporator and reactor have been distribution across the reactor volume.
heated and insulated to prevent water condensation. The system was Fig. 3 reports the measured profiles for selected representative con­
operated at ambient pressure. At the reactor bottom, a condenser allows ditions, namely for three values of space velocity at the two oven tem­
the recovery of the unreacted water (Figs. S2f in SI), while incon­ peratures of 500 and 700 ◦ C. All the experiments were characterized by
densable gases are sent to the GC (GCX, Pollution SRL, Figs. S2g in SI) the presence of a cold spot, where the bed temperature is lower than the
equipped with MolSieve and Porapack columns connected to TCD de­ oven temperature. The extent of the cold spot was affected by both the
tectors for their online quantification. A calibrated stream of N2 was GHSV and the oven temperature and it increased its magnitude at
mixed after the condenser with the reaction products in order to allow increasing total load (that is converted CH4 molar flow) of the experi­
the quantification with internal standard method. Water was calculated ment. However, the axial temperature profiles recorded in the central
according to methane consumption and CO2 production and stoichi­ and mid-radius positions were almost superimposed in all the tests,
ometries of reactions (1) and (2). The overall absolute errors detected in while a significant difference with the wall temperature was present.
carbon balances were in the range of 1–5%. This is consistent with the experimental observations and the theoretical
Temperature has been monitored with three sliding thermocouples evaluations performed in previous studies, where we addressed the
inserted in stainless steel thermowells (O.D: =3.2 mm), having the same quantitative characterization of heat transfer in conductive packed

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M. Ambrosetti et al. Catalysis Today xxx (xxxx) xxx

Fig. 1. (a) Top view graphical representation of the reactor layout with the three thermocouples; (b) top view of packed foam; (c) side view of the reactor layout.

Fig. 2. CH4 conversion as a function of oven temperature (a, left) and outlet temperature in radial position (b, right). Operative conditions: S/C ratio 4.1; GHSV:
32900, 65700 and 98600 N L h− 1 kg−cat1 (black square, red circle and blue triangle, respectively). Dotted line: equilibrium CH4 conversion. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.)

foams [21]; there, we concluded that the same reactor design herein measurements is the one proposed in Fig. 2b, where data are plotted
tested is characterized by very high axial and radial effective conduc­ against the measured outlet temperature at the mid-radius coordinate.
tivity (in excess of 20 W/m/K) [18] and a concentrated heat transfer The selection of an outlet temperature rather than an average bed
resistance at the wall (that is at the interface between the foam pe­ temperature allows for a more rigorous comparison with the chemical
ripheral surface and the inner reactor tube wall). In fact, by using a equilibrium curve, which has been calculated by the extent of reaction
lumped heat transfer model developed in [21] it was found that the method using the methane steam reforming (1) and the water gas shift
overall heat transfer coefficients of packed open-cell foams are in the (2) independent stoichiometries with DG◦ temperature functions taken
range of [400–700] W/m2/K : the wall heat transfer resistance is from literature [35]. The same standard of data representation was
responsible for over 85 % of the overall resistance. Based on these adopted throughout the kinetic study, thus making easier the qualitative
considerations, we believe legitimate to assume that across the section of evaluation of the impact of thermodynamic constraints on the observed
the foam at each axial coordinate the temperature was essentially conversions and product distributions. The representation of Fig. 2b
constant. further emphasizes that, in the ranges of space velocity herein explored,
The analysis of the temperature profiles suggests that at increasing the reactor operated mainly under a kinetically controlled regime below
flow rate the observed decline of conversion resulted from the combined 600 ◦ C (where the effect of space velocity was found), but approach to
effects of contact time and of temperature reduction. Thus, a more equilibrium influenced the high temperature behavior. On the bases of
“kinetically” informative representation of the conversion this evidence the kinetic tests described in the next section have been

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M. Ambrosetti et al. Catalysis Today xxx (xxxx) xxx

Fig. 3. temperature profiles for the different GHSV and Toven of 500 and 700 ◦ C (top and bottom, respectively). Solid line: oven set temperature; symbols with lines:
experimental temperature measurements at the bed at centerline (blue triangles), r/2 (green circles) and external wall temperature (red squares); dashed vertical
lines: position of the catalytic bed. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

1
performed at GHSV = 65700 N L h− kg-1
cat methane steam reforming, into CO2 by water gas shift. In the same
temperature range (i.e., far from the equilibrium conditions), the pro­
3.2. Kinetic analysis - experimental results ductivity of CO2 was mainly dependent on temperature but negligibly
affected by the varying feed CH4 concentration, which suggests an
After proving the heat transfer efficiency granted by the presence of overall apparent order on CO close to zero. At higher temperatures, the
the copper foams and identifying proper operating conditions that composition of the syngas closely approached the thermodynamic
enable to investigate the chemical process far from the equilibrium, the equilibrium and was characterized by the growing concentration of CO,
effects of variation of partial pressure of reactant and products were the flattening of H2 concentration and a mild negative trend of CO2
investigated. First, the effects of CH4 and H2O partial pressures were concentration with increasing temperature.
investigated in the ranges 9.75–19.50 % v/v and 40.25–90.25 % v/v, The effect of water at fixed methane concentration is then shown in
respectively. In all the tests the H2O/CH4 feed ratio was kept higher than Fig. 5.
4 to avoid coke formation. Inert N2 was fed to balance. Then, the effects The measured CH4 conversion was positively affected by the increase
of co-feed of CO and H2 were investigated. In each run, 7 different oven of water concentration, and an increase of productivity of H2 and CO2
temperatures in the range 450–750 ◦ C were tested. Overall, 10 different was observed. Instead, the outlet molar fraction of CO decreased pro­
runs (see Table S1 in SI) and 70 tests were performed. CH4 conversion in gressively at increasing water concentration; within the kinetically
Reference tests periodically repeated to verify the catalyst stability are relevant temperature-range, this was a clear evidence of the consecutive
reported in the supplementary information (see image S5). nature of water gas shift and of its positive kinetic dependence on the
The results of the runs performed at varying CH4 feed concentration concentration of water.
are plotted in Fig. 4 as a function of the bed outlet temperature measured Additional experiments were performed by enriching the methane/
at the mid-radius position. steam feed with CO and H2. Two runs were carried out with 4.9 and 7.6
It can be observed that the increase of CH4 concentration led to a % CO co-feed and the results are reported in Fig. 6. The addition of CO
decrease of conversion, suggesting an apparent global reaction order of caused an appreciable drop of CH4 conversion at the lowest tempera­
MSR less than 1. This effect is evident at temperatures below 650 ◦ C, tures, where kinetic effects prevailed.
whereas at higher temperatures the conversion data were close to 100 At 7.6 % CO co-feed, the negative effect was so important that at
%, aligned with the equilibrium. On the other hand, at the lowest tem­ 450 ◦ C heating temperature the conversion of methane was almost
peratures investigated, the production of H2, CO and CO2 was little negligible, and the test assumed the form of a water gas shift experiment,
affected; at increasing temperature, a positive effect of the reactant where about 50 % of the fed CO was converted into CO2. Indeed, the
concentration became more important. At the highest temperatures, the outlet concentration of CO passed through a minimum at increasing
concentration of products was bound by the stoichiometric and ther­ temperature, which clearly resulted from the combination of CO con­
modynamic limits. It may be concluded that the process showed an sumption by WGS and hindered CO production by MSR.
apparent reaction order in the range 0–1, growing with increasing This evidence corroborated the hypothesis that CO plays an impor­
temperature. tant inhibiting role in the kinetics of the MSR reaction on Rh. Such
Interestingly, up to 550 ◦ C, the main reaction products were CO2 and inhibiting effect had been already observed in our laboratory under
H2, which suggests a very efficient displacement of CO, produced by more diluted conditions [28,36] and by other research groups [37], who

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M. Ambrosetti et al. Catalysis Today xxx (xxxx) xxx

Fig. 4. Effect of CH4 feed concentration on: (top from left) CH4 conversion, outlet CH4 concentration, outlet H2O concentration, (bottom from left) outlet H2
concentration, outlet CO concentration, outlet CO2 concentration). Symbols: experimental measurements, dotted lines: thermodynamic equilibrium, continuous
lines: model fit. Operative conditions: GHSV 65700 N L h− 1 kg−cat1; H2O volume fraction 80.50 %; CH4 volume fractions 9.75, 14.60 and 19.50 % (red, blue and black,
respectively); N2 volume fractions 0, 4.90 and 9.75 % (red, blue and black, respectively). (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)

suggested that CO is the most abundant specie adsorbed on the catalyst to CO.
under the investigated conditions. Interestingly, the outlet H2 molar fraction responded to the com­
On the other hand, by looking at CO2 concentration, it is evident that bined effects of CO-cofeed on MSR and WGS; in fact, it decreased with
WGS activity was enhanced by increasing CO concentration from the increasing CO co-feed at temperatures below 600 ◦ C, due to the hin­
bed entrance, suggesting a positive reaction order of WGS with respect dering effect on MSR, but it increased with increasing CO content at the

Fig. 5. Effect of H2O feed concentration on: (top from left) CH4 conversion, outlet CH4 concentration, outlet H2O concentration, (bottom from left) outlet H2
concentration, outlet CO concentration, outlet CO2 concentration). Symbols: experimental measurements, dotted lines: thermodynamic equilibrium, continuous
lines: fitted values. Operative conditions: GHSV 65700 N L h− 1 kg−cat1; CH4 volume fraction 9.75 %; H2O volume fractions 40.25, 53.76, 80.50 and 90.25 % (black, red,
blue and green, respectively); N2 volume fractions 50.00, 36.49, 9.75 and 0% (black, red, blue and green, respectively). (For interpretation of the references to colour
in this figure legend, the reader is referred to the web version of this article.)

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M. Ambrosetti et al. Catalysis Today xxx (xxxx) xxx

Fig. 6. Effect of CO feed concentration: (top from left) CH4 conversion, outlet CH4 concentration, outlet H2O concentration, (bottom from left) outlet H2 concen­
tration, outlet CO concentration, outlet CO2 concentration). Symbols: experimental measurements, dotted lines: thermodynamic equilibrium, continuous lines: fitted
values. Operative conditions: GHSV 65700 N L h− 1 kg−cat1; CH4 volume fraction 14.60 %; H2O volume fractions 80.50 %; N2 volume fractions 4.90 and 0% (blue and
red, respectively); CO volume fractions 0 and 4.90 % (blue and red, respectively). (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)

highest temperatures, in line with the equilibrium of WGS. No appreciable effect was observed on conversion and product dis­
An additional experiment was performed with 9.75 % H2 co-feed tribution, indicating that the kinetics of MSR and WGS were not influ­
(run 9 in Table S1) and the results are compared in Fig. 7 and with enced by the H2 concentration. Since the catalyst was in part deactivated
those of run 10 w/o H2 in the feed, which was performed just after the H2 and no effect of H2 was found, these tests were not included in the
co-feed one, to remove the effect of moderate deactivation which was regression.
observed during the repeated standard tests (see last points in Figs. S5 of In conclusion, the experimental campaign revealed the following
SI). qualitative dependences.

Fig. 7. Effect of H2 feed concentration: (top from left) CH4 conversion, outlet CH4 concentration, outlet H2O concentration, (bottom from left) outlet H2 concen­
tration, outlet CO concentration, outlet CO2 concentration). Symbols: experimental measurements, dotted lines: thermodynamic equilibrium. Operative conditions:
GHSV 65700 N L h− 1 kg−cat1; CH4 volume fraction 9.75 %; H2O volume fractions 80.50 %; N2 / H2 volume fractions 4.90 and 0% (blue and red, respectively); H2
volume fractions 0 and 9.75 % (blue and red, respectively). (For interpretation of the references to colour in this figure legend, the reader is referred to the web
version of this article.)

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M. Ambrosetti et al. Catalysis Today xxx (xxxx) xxx

Concerning MSR, data gave evidence of: and

/ PCO2 PH2
• a reaction order with respect to CH4 in between 0 and 1, growing (1 − KP,WGS KEQ,WGS )with KP,WGS = (7)
PCO PH2O
with temperature;
• an apparent positive order of water; Kinetic and adsorption constants were re-parametrized as follows to
• an apparent negative order of CO; reduce the correlation among parameters:
• a zeroth order dependence on H2. [ ] [ ( )]
mol Eact,j 1 1
kj (T) = k0,j (T0 ) exp − − (8)
Concerning WGS, data gave evidence of: atm gcat s R T T0
[ ] [ ( )]
1 ΔHi, ads 1 1
• an apparent positive order of CO Kads,i (T) = Kads0 ,j (T0 ) exp − − (9)
atm R T T0
• an apparent positive order of H2O
• a zeroth order dependence on H2
with the reference temperature T0 = 873 K.
The model was adapted to the population of experiments and the
3.3. Kinetic analysis: data fitting kinetic parameters were estimated by minimizing the following objec­
tive function:
The kinetic analysis of experimental data was performed by ( )2 ( )2
assuming (i) a kinetic scheme consisting of the two independent re­ ∑ λexperimental − λmodel λexperimental − λmodel
fmin = MSR MSR
+ WGS WGS
(10)
actions (1) and (2), and (ii) a PFR pseudo-homogeneous non-isothermal i λexperimental
MSR λexperimental
WGS
model. The model includes the differential mass balances for the
reacting species: where λMSR and λWGS are the extents of MSR and WGS, calculated from
dFi ∑ the net molar flow changes of CH4 and CO2 across the catalytic bed.
= νi,j rj i = CH4, H2O, H2, CO, CO2 (3) The non-linear regression has been performed using Matlab routines,
dWcat
namely preliminary estimates were found by applying a genetic algo­
j

Differential mass balances were solved using the routine fsolve in rithm code (ga routine in Matlab) and optimal estimates were then ob­
Matlab. tained by applying a steepest descent method [40].
The axial temperature profiles have been assigned by fitting the Overall, 6 parameters were optimized by fitting 112 responses ob­
experimental temperature measurements of the lateral thermocouple tained in 56 independent tests.
with a 5th order polynomial (see Figs. S4 in SI), whereas radial tem­ The optimized parameter estimates are listed in Table 1 alongside
perature differences have been neglected in line with the results re­ with 0.95 confidence intervals. The correlation matrix is reported in the
ported in section 3.1. SI (Table S2).
Based on the qualitative evidence reported above, the following rate The overall fit quality can be evaluated from the parity plots in Fig. 8.
expressions were assumed for the two reactions (1) and (2): All the data fall in the ± 15 % range, which proves the adequacy of the
( / ) [ ] fit.
rMSR =
kMSR PCH4 1 − KP,MSR KEQ,MSR mol
(4) A more detailed analysis of the model adequacy is offered by the
1 + KadsCO PCO gcat s comparison between symbols and lines in Figs. 4–6.
[ ] Fig. 4 shows that by accounting for the competitive adsorption of CO
kWGS PH2 O PCO ( / ) mol
in rate expressions (4) and (5), the model adequately reproduced the
rWGS = 1 − KP,WGS KEQ,WGS (5)
1 + KadsCO PCO gcat s variable global order of the MSR (close to zero at low temperature and
Rate expression (4) reproduces the same expression proposed in a increasing in the range 0–1 with increasing temperature) as well as the
previous work [26], based on highly diluted steam reforming data ob­ apparent almost zeroth order of WGS, giving rise to an almost inde­
tained in the isothermal annular reactor; it considers a first order pendent CO2 production at varying CH4 concentration.
dependence on methane and zeroth order dependence on water in line Fig. 5, then, shows that by assuming a linear dependence of the WGS
with the intrinsic turnover rate measurements obtained by Wei and rate on H2O partial pressure (and without any direct H2O dependence
Iglesia on Rh under differential regime [25]. However, it also includes a for MSR), the enrichment of steam content in the feed was predicted to
term at the denominator accounting for the competitive adsorption of produce a positive effect on CH4 conversion and syngas production; in
CO, whose inhibiting effect was clearly demonstrated by the data ob­ fact, the promotion of rate (5) resulted in a decrease of CO concentration
tained in this and previous studies [22,28] under integral regime. throughout the bed, and in turn a beneficial mitigation of CO inhibiting
Concerning the water gas shift reaction, it is interesting to observe effect.
that in our previous studies in annular reactor and diluted feed streams The data reported in Fig. 6 were especially relevant for the estimate
[22] we had proposed a zeroth order dependence on CO and a first order of the CO adsorption constant; the effect by CO surface saturation on
dependence on water. Based on the evidence herein collected, rate both reactions allowed to obtain a fair description of the hindering of
expression (5) was modified to account for a variable order in CO, methane conversion and of the complex evolution of syngas composition
through the introduction of a linear dependence on CO partial pressure with increasing temperature; such evolution involves both the kinetic
together with a competitive adsorption term. Such an expression is in effects, prevailing in the lower temperature range, and the mass actions
line with the studies of Deutschmann and coworkers, who identified the on the high temperature thermodynamic constraints.
reaction between CO and OH as the rate determining step of the WGS
over nickel and rhodium sites [38]. The same rate determining step has
3.4. Comparison between kinetic studies under concentrated and diluted
been identified by Maestri et al. over Rh(111) sites, based on DFT studies
conditions
[39].
The reversible nature of both MSR and WGS was accounted for by
On a qualitative basis, the newly proposed MSR rate expression (4)
introducing terms of approach to equilibrium:
reproduces the same rate expression derived in 2008 by Donazzi et al.
/ PCO P3H2 [26] from highly diluted kinetic experiments in annular reactor; the
(1 − KP,MSR KEQ,MSR ) with KP,MSR = (6) WGS rate expression (5) transforms instead the original zeroth order
PCH4 PH2O
dependence on CO proposed by Pagani et al. [22] into a more

8
M. Ambrosetti et al. Catalysis Today xxx (xxxx) xxx

Table 1
Optimized kinetic parameters – all values are referred to catalyst pellet mass.
MSR 2 mol
4 EactMSR = 101.1 ± 6.56kJ/mol
kMSR (873 K) = 2.41 10− ± 1 10−
gcat s atm
WGS mol EactWGS = 51.1 ± 5.62 kJ/mol
kWGS (873 K) = 8.11 10− 2 ± 5.5 10 − 3
gcat s atm2
CO adsorption 2 1
kCO (873 K) = 2.11 10 ± 1.83 10 atm − 1 ΔHadsCO = − 32.7 ± 1.61 kJ/mol

Fig. 8. Parity plots of the extent of reactions.

comprehensive and flexible form, adequate to the newly explored con­

Table 3
ditions of high reactant concentration and CO-cofeed.
Kinetic parameters of this work: optimized kinetic parameters referred to active
A quantitative comparison between the two kinetic schemes was also
phase mass.
performed. At this scope, Table 2 reproduces the rate expressions and
MSR mol EactMSR = 101.1 kJ/mol
estimated kinetic constants of MSR and WGS from [26] and [20], kMSR (873 K) = 7.84 10− 2
gcat s atm
respectively. Notably, the kinetic expression of MSR in [26] has the same WGS EactWGS = 51.1 kJ/mol
kWGS (873 K) =
form of eq. (4) whereas the rate of WGS in [20] is reported in eq. 11.
[ ] [ ] 1 mol
2.64 10−
( / ) mol gcat s atm2
rWGS 20 = kWGS PH2 O 1 − KP,WGS KEQ,WGS σCO (11) CO adsorption kCO (873 K) = 2.11 102 atm− 1 ΔHadsCO = − 32.7 kJ/
gcat s
mol
It is important to observe that the kinetic investigations in annular
Note to Table 3. Rate expression (4) for MSR, rate expression (5) for WGS.
reactor, where the catalyst was tested in the form of an active coating
deposited onto a tubular ceramic support, provided estimates of the
passed from -37 kJ/mol in Donazzi et al. [26] to the current value of
intrinsic reaction rates for unitary washcoat mass; instead, in this work,
− 32 kJ/mol. This partly compensated the increased temperature sensi­
due to the egg-shell configuration, only a portion of the catalyst is active.
tivity of the newly proposed rate expression of MSR.
For the sake of comparison, we thus converted the kinetic parameters of
Concerning the WGS reaction, as already noted, a major formal
Table 1 into those of Table 3 by referring them to the mass of active
change from the present work is represented by the introduction of an
phase, which was calculated from the measurement of the egg-shell
explicit dependence on CO partial pressure such that the rate expression
thickness.
reproduces a variable order at increasing temperature. It is interesting to
Since the functional form of the steam reforming rate did not change,
note that the introduction of a temperature dependent CO-inhibition
it is easily appreciated that the new set of kinetic runs, operated in a
term has resulted in a lower activation energy of the revised rate
completely different experimental configuration, led to a moderate
expression by about 25 kJ/mol with respect to that estimated by Pagani
rearrangement of the parameters with a reduction of the intrinsic ac­
et al. [22].
tivity constant (kMSR) at 873 K from 1.02 to 0.78 10− 1 mol/gcat/atm and
To fully appreciate the different performances of the kinetic models,
an increase of the activation energy from 92 to 101 kJ/mol. Concerning
two cases presented in Table 4 were simulated by assuming isothermal
the CO adsorption constant, the same value was estimated at the refer­
plug-flow reactor behavior: the first case reproduces the typical
ence temperature of 873 K, while the estimated adsorption enthalpy

Table 2 Table 4
Kinetic parameters from Pagani et al. [22]. Operative conditions for comparison of representative kinetic tests performed in
annular and packed foam reactor.
MSR 1 mol EactMSR = 92 kJ/mol
kMSR (873 K) = 1.027 10− Feed composition
gcat s atm
WGS mol EactWGS = 75 kJ/mol Cases GHSV [Nl/h/kgcat]
kWGS (873 K) = 6.83 10− 3 CH4 H2O N2
gcat s atm2
CO adsorption 2
kCO (873 K) = 2.11 10 atm − 1 ΔHadsCO = − 37 kJ/mol 6
1 – Diluted conditions 2 10 0.01 0.025 0.965
2 – Concentrated conditions 2 105 0.22 0.78 0
Note to Table 2. Rate expression (4) for MSR, rate expression (10) for WGS.

9
M. Ambrosetti et al. Catalysis Today xxx (xxxx) xxx

operating conditions of the annular reactor, characterized by very high of the newly obtained kinetic scheme from concentrated to diluted feed
space velocity and highly diluted feed, the second case reproduces compositions can involve some underestimation of the CO2/CO ratio,
instead conditions close to the present experimental campaign in the especially at very short contact times.
packed foam reactor. Kinetics derived in diluted conditions (the com­
bination of MSR rate proposed by Donazzi et al. [26] and WGS by Pagani 4. Conclusions
et al. [22]) were compared with the herein presented model.
Fig. 9 shows the simulations of Case 1. Notably, under these condi­ The intensification of methane steam reforming is of paramount
tions the kinetic scheme obtained from the diluted tests in annular importance for the deployment of distributed H2 production, and the use
reactor is representative of the experimental evidence, that it the true of noble-metal catalysts coupled with conductive internals is among the
process features. Instead, the kinetic scheme obtained in this study is promising reactor solutions to overcome the heat transfer resistances
here significantly extrapolated and due to the larger activation energy and the loss of efficiency that accompany the reactor scaling-down.
for MSR, it tends to underestimate the extent of methane steam Moreover, the development of a small scale, isothermal reactor design
reforming; besides, due to the new form of WGS and the inhibiting effect offers also the opportunity to overcome the limits of the kinetic inves­
of CO adsorption, the present kinetic scheme largely underestimates the tigation, traditionally performed under diluted conditions to reduce the
extent of CO conversion into CO2. impact of temperature gradients across the catalytic bed and guarantee
It must be observed, however, that the comparison between the re­ well controlled conditions.
sponses of the two kinetic schemes at very high space velocity (as typical In this work, Rh/Al2O3 egg-shell pellets, packed in highly conducting
of the annular reactor) is extremely demanding. Cu-foams, were tested in methane steam reforming in an extensive
Fig. 10 shows then the simulations of Case 2. Here, conversely, the experimental campaign that explored the use of highly concentrated
newly proposed kinetic scheme is representative of the experimental feeds. The kinetic effects of methane, water, carbon monoxide and
evidence. However, the extrapolation of the kinetic scheme obtained hydrogen partial pressure were investigated in the absence of radial
from diluted experiments results in a large overestimation of the reac­ temperature profiles. Based on the collected evidence, a refined kinetic
tion rates, with an unrealistic full approach to equilibrium. This cannot model of MSR and WGS was proposed, which partly revisits a previously
be explained only by the moderate differences between the intrinsic rate developed scheme. The new experimental campaign substantially
constant and activation energy of MSR; instead, the linear dependence confirmed all the prevailing kinetic dependences already identified in
on H2O and the zeroth order dependence on CO of the WGS rate ex­ the past for MSR (i.e., the linear dependence on CH4 partial pressure, the
pressions in [20] result in a large overestimation of the CO− CO2 con­ irrelevance of H2O partial pressure and the inhibiting effect of CO) but
version route and, in turn, a strong mitigation of the inhibiting effect of the parameter estimates herein obtained are more robust against feed
CO on MSR. composition effects and thus suitable for the reactor design. Concerning
In practice, the adjustment of the kinetic scheme of MSR and WGS on the WGS reaction, the extension of the experimental investigation
Rh obtained in this work involves an important moderation of the re­ allowed to better capture the rate and kinetic dependences of the reac­
action rates under conditions of highly concentrated feeds. This include tion, whose accurate description is of fundamental importance to
a significant slow-down of the WGS rate (from what would be predicted correctly describe the evolutions of methane conversion and syngas
by simple extrapolation of the kinetics obtained in diluted conditions) composition, given the strong interplay between the two reactions.
that has a tremendous impact on the rate of MSR due to the inhibiting In more general terms, we herein demonstrate how, with the adop­
effect exerted by CO adsorption. It is thus concluded that extrapolation tion of conductive packed foams, it is possible to collect significant

Fig. 9. Comparison of models in Case 1: (top from left) CH4 conversion, outlet CH4 concentration, outlet H2O concentration, (bottom from left) outlet H2 con­
centration, outlet CO concentration, outlet CO2 concentration). Dotted lines: thermodynamic equilibrium, diluted kinetics red triangles, this work blue squares. (For
interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

10
M. Ambrosetti et al. Catalysis Today xxx (xxxx) xxx

Fig. 10. Comparison of models in Case 2 : (top from left) CH4 conversion, outlet CH4 concentration, outlet H2O concentration, (bottom from left) outlet H2 con­
centration, outlet CO concentration, outlet CO2 concentration). Dotted lines: thermodynamic equilibrium, diluted kinetics red triangles, this work blue squares. (For
interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

kinetic data in realistic conditions (no dilution, high conversion) in the Appendix A. Supplementary data
case of catalytic reactions with strong thermal effects. This solution can
be employed for a wide set of processes, where the strong exothermicity Supplementary material related to this article can be found, in the
or endothermicity of the reactions usually limits the feasibility of kinetic online version, at doi:https://doi.org/10.1016/j.cattod.2021.06.003.
investigations under representative conditions.
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