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 2 ( 2 0 1 7 ) 1 3 6 6 1 e1 3 6 8 0

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Sorption enhanced steam methane reforming by

NieCaO materials supported on mayenite

A. Di Giuliano a,b,*, J. Girr a, R. Massacesi b, K. Gallucci b, C. Courson a

a

University of Strasbourg, Institut de Chimie et Proc
ed
es pour l'Energie, l'Environnement et la Sant
e, UMR CNRS
7515, ECPM, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France
b
University of L'Aquila, Department of Industrial Engineering, 18 via G. Gronchi, 67100 L'Aquila, Italy

article info abstract

Article history: Sorption enhanced steam methane reforming (SESMR), i.e. SMR with in situ CO2-sorption,
Received 29 September 2016 can lead to a sustainable and economical exploiting of natural gas for hydrogen produc-
Received in revised form tion, with high purity and simultaneous sequestration of greenhouse gases. CaO-mayenite
25 November 2016 CO2-sorbents, Ni-mayenite SMR catalysts and NieCaO-mayenite combined sorbent cata-
Accepted 30 November 2016 lyst materials (CSCM) for SESMR were synthesized by wet mixing and wet impregnation
Available online 12 January 2017 methods, and characterized by means of XRD, BET/BJH, SEM/EDS, and TPR. For CSCM, an
influence of CaO load on textural and Ni reducibility properties was recorded. Materials
Keywords: sorption capacity was measured in multicycles sorption/regeneration TGA tests: it always
Sorption enhanced steam methane underwent a stabilization with cycle number increase. Reforming tests in micro-reactor
reforming scale were performed on 3 wt% to 10 wt% Ni-mayenite and selected CSCM: all Ni-
Combined sorbent-catalyst material mayenite always shown good performances, while for CSCM a detrimental role of CaO
CO2 capture load on Ni catalytic activity was evidenced.
© 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

which leads to an higher hydrogen yield, but gives also a net

Introduction CO2 production (at least 3 kg per kg of CH4 consumed) [1,16].

In recent years, concerns about consumption of fossil fuels CH4ðgÞ þ H2 OðvÞ 4COðgÞ þ 3H2ðgÞ DH0298K ¼ 206:2 kJ=mol
and greenhouse gases emissions made hydrogen one of the Reaction 1
most interesting alternatives to reach the goal of a cleaner
energy utilization [1e8]. COðgÞ þ H2 OðvÞ 4CO2ðgÞ þ H2ðgÞ DH0298K ¼ 41:2 kJ=mol
SMR (Steam Methane Reforming) is currently the main Reaction 2
route adopted in industrial scale for the production of
The enthalpy balance of Reactions 1 and 2 results in a
hydrogen, which is not available as such in nature [3,4,9,10].
strongly endothermic transformation. In fact, industrial SMR
There are different materials able to catalyze SMR, neverthe-
is an energy intensive process, typically operated at severe
less economic reasons drive the choice to Ni supported on
conditions (800e1000  C and 1.5e3.0 MPa) in a vertical array of
modified alumina catalysts [11,12]. Reaction 1 describes the
tubes filled with the catalyst, fed with methane or natural gas
actual steam reforming of methane, always accompanied by
and a stoichiometric excess of steam (inlet steam to carbon
the secondary Reaction 2 [13e15], WGS (Water Gas Shift),
molar ratio between 2.5 and 5 [17]), in order to avoid carbon

* Corresponding author. University of L'Aquila, Department of Industrial Engineering, 18 via G. Gronchi, Nucleo, Industriale di Pile, 67100
L'Aquila, Italy.
E-mail address: andrea.digiuliano@graduate.univaq.it (A. Di Giuliano).
http://dx.doi.org/10.1016/j.ijhydene.2016.11.198
0360-3199/© 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
13662 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 2 ( 2 0 1 7 ) 1 3 6 6 1 e1 3 6 8 0
deposition, which causes nickel deactivation, tubes fulfilling
and consequent pressure drop increase [12,18e20].
In order to start an effective transition towards a hydrogen
economy, it is very important to get technical improvements in
hydrogen production, so to have a reduction of its environ-
mental footprint, but this production must be kept economical,
then SMR and natural gas are still considered a relevant pro-
cess and a strategic feedstock, respectively [12]. IPCC (United
Nations Intergovernmental Panel on Climate Change) con-
siders the coupling of CCS (Carbon Capture and Storage) with
fossil fuels-based processes as a crucial approach for the lim-
itation of global warming to less than 2  C by 2100 [2,21]. IPCC
evaluated this approach together with other strategies (e.g.
energy efficiency increasing, nuclear energy, bioenergy, wind
power, solar energy) assessing various scenarios: when CCS is
excluded, only half of hypothesized scenarios brings to a global
warming lower than 2  C, anyway causing higher costs than
those predicted when CCS is included (138% more expensive
on average) [2,21]. For these reasons, a good candidate for the
sustainable conversion of natural gas in high purity hydrogen
is SESMR (Sorption Enhanced Steam Methane Reforming), that
is to say the coupling of traditional SMR with an in situ CO2
capture, carried out by a high temperature solid sorbent
[12,22e24]. This solid sorbent pushes WGS (Reaction 2) equi-
librium, and then SMR (Reaction 1), towards supplementary
hydrogen production by subtracting CO2 from the gaseous re-
action phase, i.e. the so called sorption enhancing [1,17,25].
When the sorbent is saturated, it can be regenerated in
different temperature conditions than those of SESMR, pro-
ducing highly concentrated or pure CO2, ready for other
disposal strategies [2,26] or as a chemical feedstock (e.g. for
synthesis of methanol or dimethyl ether [27,28]).
SESMR, from the solid's point of view, is a cyclic alternation
of CO2-sorption and sorbent regeneration sessions: a suitable
reactor configuration is the double fluidized circulating bed,
with one reactor operated as a reformer and the other as a
sorbent regenerator [23,29]. As a consequence, a CO2-sorbent
for SESMR should have a high CO2-sorption capacity and rate,
a regeneration temperature window relatively close to
reforming conditions, and a stable CO2-sorption capacity
during capture/regeneration multicycles [17]. Several high
temperature solid sorbents have been studied, including CaO-
based sorbents, lithium zirconates, lithium orthosilicates,
sodium zirconates, other ceramic materials based on lithium
[17,30]. Among them, CaO-based ones are the most used
because they assure: (i) satisfactory CO2-sorption capacity and
rate [31]; (ii) carbonation (Reaction 3) at 600e700  C and at
atmospheric pressure, conditions compatible with a simulta-
neous catalytic SMR conversion; (iii) calcination (reverse of
Reaction 3) at 800e950  C and at atmospheric pressure, tem-
peratures relatively close to those of carbonation [32,33].
CO2ðgÞ þ CaOðsÞ 4CaCO3ðsÞ DH0298 K ¼ 178:2 kJ=mol
Reaction 3
Nevertheless, when the stability of CO2-sorption capacity
during carbonation/calcination multi-cycles is considered,
CaO-based sorbents require more careful evaluations: in fact,
CO2-sorption capacity of CaO undergoes a strong reduction
with cycle number increase [30,34e36]. According to
literature, this is mainly due to sintering and, in order to limit
this phenomenon, CaO can be integrated with an inert sup-
port in an heterogeneous solid porous structure [17,30,37e39].
Among possible supports, mayenite (Ca12Al14O33) [40,41] and
other calcium aluminates (e.g. Ca9Al6O18, Ca3Al2O6) are largely
employed as CaO binder in synthetic materials [17,30,37].
As far as SESMR with a CaO-based sorbent is concerned, the
methane conversion is less energy intensive than in SMR,
thanks to the enthalpy compensation between Reactions 1, 2
and 3, which gives an approximately auto-thermal process
[23,42e44]. Moreover, from an exergetic point of view, SESMR
and consequent sorbent regeneration are more advantageous
than SMR and relative downstream purification processes,
needed to get the same hydrogen yield [26,43]. Different studies
prove the feasibility of SESMR with system containing raw
mixing of solo-catalyst and solo-sorbent particles
[11,33,45e48]. In order to avoid inter-particle and intra-particle
diffusivity resistances [49e52] and to allow a more intimate
mutual compensation between endothermic and exothermic
reactions, the concept of CSCM (Combined Sorbent Catalyst
Materials), i.e. a single particle with a CO2-sorption phase and a
SMR catalytic active phase, has been proposed [22]. Further-
more, the use of CSCM instead of equivalent solo-catalyst plus
solo-sorbent system, drastically reduces the total solid hold-up
in the reactor. In this framework, various syntheses for
NieCaOeCaxAlyOz CSCM and correspondent experimental
performances are reported in literature [1,46,53e55].
In this paper, we focus on CSCM for SESMR constituted by
mayenite associated with Ni and CaO (i.e. NieCaO-mayenite),
and on correspondent materials with only SMR catalytic
function (i.e. Ni-mayenite) or only CO2-sorption function (i.e.
CaO-mayenite). These materials are synthesized, character-
ized and experimentally tested for steam reforming in micro-
reactor scale.
Materials and methods
Synthesis
Two subsequent synthetic routes constitute the overall method
applied to produce CSCM studied in this work: wet mixing, for
preparation of sorbent phase containing calcium and
aluminum, and wet impregnation, for addition of catalytic
phase containing nickel. Chemical precursors used in laboratory
scale syntheses are: Ca(CH3COO)2$xH2O (ACROS ORGANICS,
purity ¼ 99%, x experimentally determined) for calcium;
Al(NO3)3$9H2O (SIGMAeALDRICH, purity > 98%) for aluminum;
Ni(NO3)2$6H2O (SIGMAeALDRICH, purity > 97%) for nickel.
Wet mixing
Wet mixing is a modification of the method described by
Zamboni et al. [56], which is also a modification of a method
previously published by Li et al. [57]. The choice of proper
masses of Ca and Al precursors salts determines the free CaO
fraction in the final product: a molar ratio Ca/Al ¼ 6/7 brings
nominally to mayenite while higher ratio produces CaO-
mayenite sorbent.
Hereinafter, wet mixing products are named as CaOy,
where y is the nominal weight percentage of free CaO
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 1 3 6 6 1 e1 3 6 8 0
associated to mayenite (e.g. CaO0 is nominally mayenite,
CaO30 is nominally composed by 30 wt% of free CaO and 70 wt
% of mayenite, according to masses of precursor salts).
Wet mixing steps are:
1. Calcination of Ca(CH3COO)2$xH2O, in order to obtain CaO,
by a 3  C min1 heating ramp up to 750  C and a plateau for
4 h at 750  C;
2. Solubilization of Al(NO3)3$9H2O in stirred distilled water
and addition of CaO powder in this solution. The initial
volume of the whole mixing is 10 ml per gram of desired
product, to be halved by stirring and heating at 70  C;
3. Drying of resulting slurry for 12 h at 120  C;
4. Calcination of dried solid by a 3  C min1 heating ramp up
to 750  C and a plateau for 4 h at 750  C;
5. Hydration of calcined solid, with 1 ml of distilled water per
gram of solid, reduced in granules in the dimensional order
of the millimeter before water addition;
6. Drying of hydrated solid for 12 h at 120  C;
7. Calcination of dried solid by a 3  C min1 heating up to
900  C and a plateau for 1.5 h at 900  C.
Wet impregnation
Wet impregnation is a modification of the method described
by D'Orazio et al. [58] and by Micheli [59]. It is applied on wet
mixing products CaOy. Its aim is to add on them a desired
quantity of metallic nickel, by tuning the mass ratio between
CaOy and the nickel salt precursor. If wet impregnation is
applied on CaO0, the product is a Ni-mayenite catalyst for
SMR. If it is applied on a CaO mayenite sorbent (CaOy with
y > 0), one obtains a CSCM for SESMR.
Hereinafter, wet impregnation products are named as
CaOyNiz, where z is the nominal weight percentage of metallic
nickel in the final reduced product.
Wet impregnation steps are:
1. Solubilization of Ni(NO3)2$6H2O in stirred distilled water
and then addition in this solution of granular CaOy (particle
in the order of the millimeter). The initial volume of this
mixing is 10 ml per gram of desired product, to be halved by
stirring and heating at 70  C;
2. Drying of resulting slurry for 12 h at 120  C;
3. Calcination of dried solid by a 3  C min1 heating ramp up
to 900  C and a plateau for 4 h at 900  C.
Characterization
Characterization of synthesized materials consists in the
application of XRD (X-Ray Diffraction) for crystalline phase
detection, BET (BrunauereEmmetteTeller) and BJH (Bar-
retteJoynereHalenda) methods for porosimetry, SEM/EDS
(Scanning Electron Microscopy combined with Energy
Dispersive X-ray Spectrometry) for morphological observa-
tions, TPR (Temperature Programmed Reduction) for reduc-
ibility properties, and TGA (Thermo-Gravimetric Analysis) for
CO2-sorption properties.
XRD
XRD spectra are recorded by X-ray diffractometer BRUCKNER
AXS D8 ADVANCED using CuKa radiation to detect crystalline
13663
phases. Phase identification is performed by comparison with
JCPDS (Joint Committee on Powder Diffraction Standards) files.
Spectra are recorded in a 2q range from 20 to 70 , with a scan-
ning step equal to 0.0158 and a sampling time of 1 s per step.
Acquired XRD spectra are also used for the estimation of
Ca12Al14O33 and CaO average crystallite sizes (L), by Scherrer
equation [60,61] (Equation (1)). Constants K ¼ 0.9 and
l ¼ 1.5406 Å (wavelength of CuKa radiation) are assumed,
while FWHM (Full Width at Half Maximum, in radiant) and
correspondent Bragg angle (2q, in radiant) are measured on
the ray at about 33 for Ca12Al14O33 and on that at about 64 for
CaO, because they are those assuring no overlapping with rays
of other phases in all samples.
h i

K$l A
L½nm ¼ (1)
10$FWMH½rad$cosð2q½radÞ
Porosimetry
A MICROMETRICS ASAP 2420 analyzer implements BET and
BJH methods, recording N2 adsorption and desorption iso-
therms at 196  C for each solid sample, i.e. 100 mg of a
powder with particle diameter in the range from 100 mm to
125 mm, previously degassed at 250  C for 8 h at least. Quan-
tities considered in this paper are BET specific surface and BJH
pore specific volume from desorption isotherm.
SEM/EDS
SEM micrographs are recoded by a PHILIPS XL30CP device.
Operative conditions are: high tension at 20 kV, detector in
BSE (Back Scattering Electron) mode and vacuum in control-
pressure mode. For elemental composition analyses by EDS,
the SEM PHILIPS XL30CP is equipped with an OXFORD ENERGY
250 device, containing an INCAx-act LN2-free detector.
Samples in the form of powder are observed and analyzed
externally. Moreover, powders are embedded in Buehler
Epoxycure bi-component epoxy resin and then polished with
diamond suspensions, for internal cross sectional area
analyses.
TPR
A MICROMETRICS AUTOCHEM II analyzer performs TPR. The
sample, i. e. 100 mg of a powder with particle diameter in the
range from 100 mm to 125 mm, is placed in a quartz packed bed
reactor. Before the actual TPR, a TPD (Temperature Pro-
grammed Desorption) is operated, in order to clean adsorbed
gases and decompose contingent CaCO3 or Ca(OH)2 in the
sample, due to room atmosphere exposure. TPD steps are a
15  C min1 heating ramp up to 750  C, a plateau at 750  C for
30 min and a cooling down to room temperature, all under an
Ar stream of 50 Nml min1. After that, actual TPR starts, with a
15  C min1 heating ramp up to 1000  C and a plateau at
1000  C for 30 min, under a reductive stream (10 vol% of H2 in
Ar) of 50 Nml min1.
TGA
A LINSEIS L81 device is used for TGA. Two kind of test are
performed: a long term CO2-capture and a multicycles CO2-
capture/regeneration.
In both, a mass of the sample in the range from 30 mg to
100 mg, with particle diameter in the range from 38 mm to
13664 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 2 ( 2 0 1 7 ) 1 3 6 6 1 e1 3 6 8 0
100 mm, undergo a preliminary treatment: a 10  C min1
heating ramp up to 800  C, a plateau for 30 min at 800  C and a
cooling down to 650  C, all under 280 Nml min1 of N2, with the
same purpose of TPD described in Section TPR.
In the long term CO2-capture test, the sample stays for 7 h
at 650  C under 330 Nml min1 of a gaseous stream containing
15 vol% of CO2 in N2. This duration is assumed to be sufficient
for the conversion of the actual available CaO in the sample to
CaCO3, permitting to calculate its maximum sorption capacity
by the measured mass increase, with respect to the mass at
the end of the preliminary treatment. In fact, the actual
available CaO should be different from the nominal one
because of: (i) the diffusional effect in a typical shrinking core
reaction [62] and (ii) Ca combination in contingent crystalline
phases.
In the multicycles CO2-capture/regeneration test, the
sample stays for 30 min in the same conditions of the long
term CO2 capture test, converting CO2 and CaO in CaCO3.
Then, it undergoes a regeneration with the same procedure of
the preliminary treatment. The alternation of these two pha-
ses continues for 50 times, and for each one captured CO2 is
estimated from the measured mass increase during the
30 min CO2-capture session, with respect to the mass at the
end of the preceding regeneration. The 50th cycle ends with
the CO2-capture session, in order to obtain a carbonated
sample for further evaluations.
Conditions for this characterization method are those
adopted by Zhou et al. [63], chosen from the exhaustive review
of Shokrollahi Yancheshmeh et al. [17], where tests with
regeneration in pure CO2 or CO2 and inert gases solutions at
higher temperatures are also reported. Among these, an
example evidencing detrimental role of regeneration with CO2
on sample stability is that of Li et al. [57,64]: their CaO-
mayenite with 75 wt% of free CaO had a sorption capacity of
41 g/100 g of sorbent after 50 cycles with mild regeneration
conditions (850  C, 100 vol% N2), decreased to 22 g/100 g of
sorbent after 56 cycles with a harder regeneration (980  C,
100 vol% CO2) [17].
Fig. 1 e Laboratory scale test rig for steam reforming catalytic tests.
Catalytic tests
Fig. 1 schematizes the experimental equipment used to
operate catalytic tests. The packed bed quartz reactor (inter-
nal diameter 7 mm) contains the sample (particle diameter
from 100 mm to 125 mm) supported by quartz wool. This reactor
is located in a cylindrical electric furnace, controlled by a
thermocouple placed within the sample packed bed. Inlet
gaseous flowrates (H2, CH4, N2 as internal standard, Ar as
diluent) are regulated by mass flow controllers. Liquid distilled
water is pumped by an HPLC micro-pump GILSON 350, which
controls liquid volumetric flowrate, in an evaporation cham-
ber at 280  C where resulting steam and all other gases mix
together before entering in the reactor. Downstream to the
reactor, a water trap cooled with ice works as a condenser,
separating unreacted water before product gases enter in
analyzers. These are two GC (Gas Chromatographs) in series
equipped with TCD (Thermal Conductibility Detector). The
first GC is an AGILENT 7890A, with a molecular sieve capillary
column, and detects H2, N2, CH4, CO. The second GC is a DELSI
INSTRUMENT Di200, with a packed polymeric column,
detecting CO2. Products flowrates are calculated by measured
concentrations, thanks to the internal standard N2 (Equation
(2)), of which flowrate is considered constant across the whole
process.
cGCi;out
Fi; out ¼ FN ;in ; i ¼ CH4 ; H2 ; CO; CO2 (2)
cGCN2 ;out 2
This test rig is used for SMR tests on Ni-mayenite catalysts
and for SESMR on NieCaO-mayenite CSCM. Atmospheric
pressure in the reactor, net of pressure drops, is a constant
condition in all tests.
SMR on Ni-mayenite catalysts
The sample mass is in the range from 200 mg to 500 mg.
First of all, a pre-reduction procedure is necessary, since
NiO in the as-synthesized sample must be converted in
metallic nickel, the active phase for steam reforming
 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 2 ( 2 0 1 7 ) 1 3 6 6 1 e1 3 6 8 0 13665

catalysis. Pre-reduction counts a 10  C min1 heating ramp up
to 900  C and a plateau at this temperature for 1 h, under the
following inlet flows: 2.8 Nml min1 of H2, 2 Nml min1 of N2
and 9.2 Nml min1 of Ar, corresponding to 20 vol% of H2. After
that, the reactor is cooled under an Ar stream, down to the
temperature chosen for the reforming.
Two different procedures for the regulation of SMR tem-
perature are applied:
 SMR-procedure1: SMR is operated at 850  C for 1 h, then at
750  C for 1 h and in the end at 650  C for 1 h. During the
whole process, the inlet molar steam/carbon ratio is equal

Fig. 2 e XRD comparisons between CSCM and their parent sorbents. Detected phases: Ca12Al14O33 (JCPDS 09-0413); CaAl2O4
(JCPDS 70-0134); CaO (JCPDS 37-1497); NiO (JCPDS 47-1049); Ca(OH)2 (JCPDS 44-1481).
13666 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 2 ( 2 0 1 7 ) 1 3 6 6 1 e1 3 6 8 0

Table 1 e Crystallite average size (L), estimated by Scherrer equation (Equation (1)) [60,61].
Ca12Al14O33 CaO
Material As-synthesized After-TPR As-synthesized After-TPR
L [nm] L [nm] L [nm] L [nm]
CaO0 37 e 16 e
CaO0Ni3 36 39 18 21
CaO15 33 e 23 e
CaO15Ni3 39 40 18 23
CaO30 30 e 16 e
CaO30Ni3 34 38 20 23
CaO45 31 e 24 e
CaO45Ni3 31 37 20 25
CaO54 32 e 24 e
CaO54Ni3 35 38 28 29

Fig. 3 e Effects of wet impregnation in order to obtain 3 wt% of Ni in the reduced final product on pore properties: a) BET
specific surface; b) BJH pore specific volume.
 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 2 ( 2 0 1 7 ) 1 3 6 6 1 e1 3 6 8 0 13667

to 3 and inlet gas flows are: 2 Nml min1 of CH4,
2 Nml min1 of N2 and 10 Nml min1 of Ar.
 SMR-procedure2: after SMR-procedure1, reactor is cooled
down to room temperature and then heated up to 650  C
under Ar; at 650  C SMR is newly started by feeding again
the same flows, as in SMR-procedure1.
The aim of these two procedures is to search differences in
the catalytic activity of nickel at 650  C, the temperature of
interest for SESMR with CSCM, depending on the way this
temperature is approached: in SMR-procedure1 the reforming
has been already started before reaching 650  C, while in SMR-
procedure2 it is triggered exactly at 650  C.
SESMR on NieCaO-mayenite CSCM
The sample mass is 500 mg. Pre-reduction step described in
Section SMR on Ni-mayneite catalysts is applied for CSCM
too. After that, the reactor is cooled down to 650  C under an
inert Ar stream, and at this temperature reforming starts by
the switch from the inert Ar stream to the same inlet flows of
SMR in Section SMR on Ni-mayneite catalysts for steam, CH4,
N2, Ar.
Equilibrium simulations
In the process simulation environment CHEMCAD® 6.5, a
Gibbs Free Energy Reactor UnitOp in isothermal mode is used
for calculations of equilibrium compositions corresponding to

Fig. 4 e SEM micrographs with a 2000£ magnification: a) CaO30; b) CaO30Ni10; c) CaO54; d) CaO54Ni10.

Fig. 5 e EDS mapping on SEM micrograph of CaO30Ni3 cross sectional surface: a) elemental Al; b) elemental Ca; c) elemental
Ni.
13668 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 2 ( 2 0 1 7 ) 1 3 6 6 1 e1 3 6 8 0

experimental conditions described in Sections SMR on Ni-
mayneite catalysts and SESMR on Ni-CaO-mayneite CSCM,
including CH4, H2O, CO, CO2, H2, Ar, N2, CaO, CaCO3 in the
component list.
Results and discussion
Textural properties and crystalline phases in as-synthesized
materials
XRD patterns in Fig. 2 show effectiveness of wet mixing method
in the production of CaO-mayenite sorbents and of wet
impregnation in adding nickel on wet mixing products as NiO,
since the last step of the method is a calcination at 900  C.
Nevertheless, traces of undesired crystalline phases are detec-
ted too. CaAl2O4 is a calciumealuminate phase in equilibrium
with Ca12Al14O33 up to 1390  C for Ca/Al molar ratio between 6/7
and 1/2 [40]. It appears in CaO0, CaO15 and CaO30, while it does
not in CaO45 and CaO54. One can infer that the higher the
desired free CaO excess, the easier the involving of Al and Ca in
Ca12Al14O33 formation. In fact, in CaO0 there is some unreacted
CaO too. Ca(OH)2 in CaO30 and CaO45Ni3 surely descends from
high reactivity between atmospheric moisture and CaO.
In Table 1, estimation of crystallite sizes by Scherrer
equation (Equation (1)) are resumed: average crystallite size of
as-synthesized samples is between 30 nm and 39 nm for
Ca12Al14O33 phase, between 16 nm and 28 nm for CaO phase.
These two quantities are comparable within each sample, so a
similar dispersion between the two phases can be assumed.

Fig. 6 e EDS mapping on SEM micrograph of CaO30Ni10 cross sectional surface: a) elemental Al; b) elemental Ca; c) elemental
Ni.

Fig. 7 e EDS mapping on SEM micrograph of CaO30Ni10 cross sectional surface, with partially dispersed Ni: a) elemental Al;
b) elemental Ca; c) elemental Ni.
 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 2 ( 2 0 1 7 ) 1 3 6 6 1 e1 3 6 8 0 13669

The lattice parameter (a) of the cubic face centered structure
of CaO (4.81 nm) and the cubic body centered structure of
Ca12Al14O33 (11.98 nm) are also calculated and reported (Table
1). These parameters are constant in all samples.
Wet impregnation brings modifications on textural prop-
erties too, as shown in Fig. 3. In this picture materials are
grouped in couples, each formed by a parent CaO-mayenite
sorbent and its correspondent impregnated NieCaO-mayen-
ite, i.e. material before and after wet impregnation. Two
different behaviors, according to free CaO fraction in the
parent sorbent, can be inferred: for 15 wt% or less, wet
impregnation gives an increase in BET specific surface (Fig. 3a)
and BJH pore specific volume (Fig. 3b); on the contrary, for
30 wt% or more, these quantities have a decrease after wet
impregnation. Then, wet impregnation (composed by
hydration and calcination at 900  C) affects more especially
textural properties of mayenite than CaO phase (Fig. 3a).
SEM micrographs on powder samples do not evidence
particular modifications before and after wet impregnation in
their granular solid structure. An example is given (Fig. 4) for
some samples: CaO30, CaO30Ni10, CaO54, and CaO54Ni10.
EDS on external surfaces show an inhomogeneous distri-
bution of nickel in impregnated samples and zones with
different Ca/Al ratios on the same particle, in agreement with
the desired concept of a free CaO phase supported on calcium
aluminates. SEM micrographs and EDS mapping on inner
cross sectional surfaces of embedded samples can better
explain the inhomogeneity of nickel distribution: for all
examined materials, elemental nickel detected by EDS is
mainly concentrated in thin shells laying on external particle

Fig. 8 e H2 consumption as a function of temperature during TPR of impregnated materials with 3 wt% of Ni.

Fig. 9 e H2 consumption as a function of temperature during TPR of impregnated materials with 10 wt% of Ni.
13670 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 2 ( 2 0 1 7 ) 1 3 6 6 1 e1 3 6 8 0

surfaces (examples in Figs. 5 and 6) or in lodes placed in par- 450  C on alumina supports [67], so it can be inferred that in
ticle internal voids (an example in Fig. 6). Elemental Al, Ca and our materials nickel is highly stabilized by CaO-mayenite of
O are also detected in these shells or lodes. A partial disper- the first family, and moderately stabilized by CaO-mayenite
sion of Ni can be found only in the case of materials with 10 wt supports of the second, probably due to excess of CaO that
% of Ni (an example in Fig. 7). It is worth to stress here that the hinders the stronger interactions between Ni and mayenite,
situations of Figs. 6 and 7 belong to the same sample observed in CaO0Ni3 and CaONi10.
(CaO30Ni10). Moreover, materials in Figs. 5, 6 and 7 arise from The stabilizing effect of CaO and other alkali earths on
wet impregnation on the same CaO-mayenite sorbent (CaO30), NiO reduction over alumina supports is reported extensively
then Ni fraction influences its dispersion. by Richardson et al. [68]. For Lemonidou et al. [69], nickel
reduction peaks for temperature higher than 750  C are
attributed to the conversion of the stable spinel phase
Reduction properties NiAl2O4 to Ni, Al2O3 and H2O, while peaks under this tem-
perature are attributed to reduction of nickel oxides. In XRD
The nature of the support and its reactivity towards reducible spectra of our samples before and after TPR, the only
elements, in our case nickel, have a key role on reducibility detectable crystalline phase modification is the reduction of
properties [65]. H2 consumption peaks in TPR profiles depict a
chart for energies of different bonds between the reducible
element and its environment: the stronger the element-
Table 2 e Experimental and nominal CO2-sorption
support interactions (i.e. the more the element is stabilized by
capacities estimated by long term CO2-capture test in
the environment), the higher the temperature of reduction [66]. TGA.
Figs. 8 and 9 show H2 consumption profiles during TPR of
Experimental Nominal
materials impregnated with 3 wt% and 10 wt% of Ni. These
CO2-sorption capacity CO2-sorption capacity
profiles divide our materials in two families on the basis of the Material
[g of captured [g of captured
free CaO content in their parent sorbent. The first family,
CO2/100 g of material] CO2/100 g of material]
NieCaO-mayenite deriving from wet impregnation of CaO0
and CaO15, has the highest reduction temperature beyond CaO30 27.3 23.6
CaO30Ni3 20.9 22.9
800  C. The second, NieCaO-mayenite deriving from wet
CaO54 41.3 42.4
impregnation of CaO30, CaO45, CaO54, has a preponderant CaO54Ni3 36.1 41.2
part of the whole H2 consumption at temperatures lower than
750  C. Free NiO is normally reduced at temperature around

Fig. 10 e XRD comparison between CSCM before and after TPR. Detected phases: Ca12Al14O33 (JCPDS 09-0413); CaAl2O4
(JCPDS 70-0134); CaO (JCPDS 37-1497); NiO (JCPDS 47-1049); Ni (JCPDS 65-2865); Ca(OH)2 (JCPDS 44-1481).
 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 2 ( 2 0 1 7 ) 1 3 6 6 1 e1 3 6 8 0 13671

Fig. 11 e Evolution of CO2-sorption capacity during multicycles CO2-capture/regeneration test in TGA.

Fig. 12 e XRD comparisons between CaO54 and CaO54Ni3 before and after TGA multicycles CO2-capture/regeneration test.
Detected phases: Ca12Al14O33 (JCPDS 09-0413); CaO (JCPDS 37-1497); NiO (JCPDS 47-1049); CaCO3 (JCPDS 05-0586).
13672 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 2 ( 2 0 1 7 ) 1 3 6 6 1 e1 3 6 8 0

NiO to Ni0 (some examples in Fig. 10), while NiAl2O4 or Al2O3

Table 3 e Equilibrium values for SMR and SESMR at
are never detected. In addition, EDS analyses on cross
different experimental conditions, calculated by
CHEMCAD® 6.5 simulations; constant values are sectional SEM micrographs revealed that nickel shells are
P ¼ 1 atm, inlet steam to carbon molar ratio ¼ 3, CaO/CH4 mainly adherent to layers richer in Al in the first family, and
molar ratio ¼ 8.5. in Ca for the second (Fig. 5). So the different reduction
T Ci,out properties among these two families, in our case, can be only
related to the different ratios between free CaO and calcium
 [vol% dry diluent free]
[ C]
aluminates in the support. The lower free CaO fraction, the
CH4 H2 CO CO2 higher reduction temperature.
SMR 850 0.0 76.8 16.0 7.2 Some increase in crystallite size (L) is observed for all
SMR 750 0.1 77.1 14.1 8.7 samples after TPR (Table 2).
SMR 650 0.8 77.0 11.5 10.7
SESMR 650 0.1 97.9 0.4 1.6

Table 4 e Conditions and CH4 conversions in SMR tests.

Material Ni [wt%] WHSV Ni-WHSV cCH4 SMR-procedure1 cCH4 SMR-procedure2
½NlCH4 ;in h1 gcat 1  ½NlCH4 ;in h1 gNi 1    
At 850 C [%] At 750 C [%] At 650 C [%] At 650  C [%]
CaO0Ni10 10.0 0.24 2.4 100.0 100.0 97.8 96.4
CaO0Ni6 6.0 0.24 4.0 100.0 99.6 96.7 96.5
CaO0Ni4.5 4.5 0.24 5.3 100.0 100.0 97.3 97.1
CaO0Ni3 3.0 0.24 8.0 100.0 99.5 96.7 96.2
CaO0Ni3 3.0 0.54 18.1 100.0 99.0 82.2 77.9

Fig. 13 e Product gas composition in SMR tests with 500 mg of CaO0Ni3: a) SMR-procedure1; b) SMR-procedure2.
 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 2 ( 2 0 1 7 ) 1 3 6 6 1 e1 3 6 8 0 13673

CO2-capture properties
Table 5 e Conditions and CH4 conversions in SESMR tests
(WHSV ¼ 0.24 NlCH4 ;in h1 gcat 1 ).
In Table 2 experimental CO2-sorption capacities, obtained by
Material Ni Ni-WHSV cCH4 at
long term CO2-capture tests, and nominal ones, based on the
[wt%] ½NlCH4 ;in h1 gNi 1  650  C [%]
precursors masses used in the synthesis, are compared. In
both cases, the sorption capacities of impregnated materials CaO15Ni3 3 8.0 95.0
CaO30Ni3 3 8.0 From 48.8 to 11.9
are lower than those of their parent sorbents, but in the case of
CaO54Ni3 3 8.0 From 39.5 to 10.1
experimental values this cannot be quantitatively attributed CaO30Ni10 10 2.4 95.3
only to the reduction of the nominal weight fraction of CaO in CaO54Ni10 10 2.4 96.7
the CSCM, as for nominal ones. Possible causes for this
experimental reduction are: (i) partial physical CaO removal in
the first step of wet impregnation (Section XRD); (ii) shadow-
ing effect of nickel-calcium-aluminum shells formed in CSCM surface and BJH specific volume before and after wet
(Fig. 5). impregnation (Fig. 3). For CaO54 and CaO54Ni3, an evident
Fig. 11 resumes CO2-sorption capacity evolution during decay in CO2-sorption capacity is recorded in the first fifteen
multicycles CO2-capture/regeneration tests. In all cases pre- cycles. For CaO30 it is smaller, and absent in CaO30Ni3. Any-
sented in Fig. 11, sorption capacity of the CSCM is always way, after the twentieth cycle a substantial stabilization
minor than the one of the correspondent parent sorbent, happens. This confirms the good influence of an inert binder,
confirming trends pointed by long term tests (Table 2). This in our case mayenite, in the hindering of CaO's sorption ca-
can be imputed to the same phenomena described just above pacity decay in CO2-capture/regeneration cycles, with regen-
in the commentary of Table 2 and to variations of BET specific eration under inert gas flow [17,30,37,56].

Fig. 14 e Product gas composition in SMR tests with 200 mg of CaO0Ni3: a) SMR-procedure1; b) SMR-procedure2.
13674 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 2 ( 2 0 1 7 ) 1 3 6 6 1 e1 3 6 8 0

Fig. 15 e Product gas composition in SESMR tests with 500 mg of: a) CaO54Ni3; b) CaO30Ni3.

Fig. 16 e Product gas composition in SESMR tests with 500 mg of CaO15Ni3.

 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 2 ( 2 0 1 7 ) 1 3 6 6 1 e1 3 6 8 0
An indication of reactivity in CO2 capture can be inferred
for each material, by a comparison between its CO2 sorption
capacity during multicycle test and the value from long term
one (considered as the upper limit). CaO54 exhibits a sorption
capacity equal to 69% of its long term one at the 1st cycle,
decreased to an averaged value between 20th and 50th cycle of
47%. Analogously, CaO54Ni3 starts from 53%, arriving to an
average of 25% and CaO30 goes from 76% to 57%. CaO30Ni3
maintain a stable 64% for both 1st cycle and average between
20th and 50th.
As reported in the literature by Stanmore and Gilot [70], the
carbonation reaction took place in two stages: an initial rapid
rate is followed by a slower approach to a conversion plateau
[71] and different limestone materials don't return to 100%
conversion [72]. This behavior can be explained by the
increasing formation of calcium carbonate layer (molar vol-
umes is 36.9 cm3/mol for CaCO3 and 16.9 cm3/mol for CaO) on
the CaO grain, increasing diffusion resistance between CO2
and reactive CaO grain surface. The effect of diffusion resis-
tance, due to carbonate product layer, on the reaction rate can
Fig. 17 e Product gas composition in SESMR tests with 500 mg of: a) CaO54Ni10; b) CaO30Ni10.
13675
be well predicted by applying the shrinking core model at a
single calcium containing grain [73,74]. The shrinking core
model hypothesizes that reaction occurs in the outer coat of
the grain and a thin reaction front is formed, moving towards
the particle center, in accordance with SEM micrographs
presented by Garcı́a-Labiano et al. [75] and by Gallucci et al.
[62], showing a well evident porous structure constituted by
CaCO3 grains (1e2 mm average size).
XRD spectra on carbonated samples obtained at the end of
multicycles CO2-capture/regeneration tests confirm the for-
mation of CaCO3 and evidence the uncomplete conversion of
CaO for both CSCM and their parent sorbents (an example in
Fig. 12).
Catalytic tests
Test conditions are expressed in terms of WHSV (Weight
Hourly Space Velocity (Equation (3)), and Ni-WHSV (Nickel
Weight Hourly Space Velocity) (Equation (4)):
13676 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 2 ( 2 0 1 7 ) 1 3 6 6 1 e1 3 6 8 0

FCH4 ;in For CSCM descending from CaO54 (Fig. 15a) and CaO30
WHSV ¼ (3)
m (Figure 15b), 3 wt% of Ni is not sufficient to maintain a stable
F CH4 conversion in explored conditions (Table 5), so neither a
Ni  WHSV ¼  CH4 ;in  (4)
m$ wNi 100
= sorption enhancing nor a satisfactory and stable catalytic
activity are achieved.
Catalytic performances are compared by CH4 conversion
On the other hand, a 3 wt% of Ni is sufficient in CSCM
(Equation (5)) and by concentrations on dry and diluent-free
descending from CaO15 (Fig. 16) which assure a CH4 conver-
basis (Equation (6)):
sion of 95.0% under the same conditions (Table 5). Moreover,
FCH4 ;in  FCH4 ;out the catalytic activity is stable during, at least, 3 h. During the
cCH4 ¼ $100 (5)
FCH4 ;in first 20 min of test, sorption enhancing assures a higher
hydrogen concentration (90 vol% on dry and diluent-free
Fi;out basis) than after sorbent saturation (77 vol% on dry and
ci;out ¼ P $100; i; j ¼ CH4 ; H2 ; CO; CO2 (6)
j Fj;out
diluent-free basis), because of the CO2 sorption and the related
shift of the reactions towards H2 production. A slight decrease
Equilibrium values for these concentrations are calculated
in CH4 conversion can be observed from 96.7% during SESMR
by CHEMCAD® 6.5 simulations at our experimental conditions
to 94.9% after sorbent saturation.
(Table 3).
For CSCMs descending from CaO54 (Fig. 17a) and CaO30
(Fig. 17b), 10 wt% of Ni on the respective CaO-mayenite sor-
SMR catalyzed by Ni-mayenite bents gives rise to a catalytic activity high enough to sustain
Table 4 resumes SMR catalytic test results and correspondent
firstly SESMR and, after sorbent saturation, SMR too. For the
experimental conditions. CaO54Ni10, SMR thermodynamic values (Table 3) are reached
As far as SMR-procedure1 is concerned, CH4 conversion is after, at least, 120 min of test because of a very slow sorbent
total at 850  C and almost total at 750  C for all the samples, saturation. For the CaO30Ni10, during first 20 min of test
containing between 3 and 10 wt% of Ni. It appears that at these
SESMR can be identified by concentration profiles of H2, CO
reaction temperatures and with a WHSV of
and CO2, then gas composition reaches SMR thermodynamic
0.24 NlCH4 ;in h1 gcat 1 , 3 wt% of Ni is sufficient to obtain total
values and remains stable until, at least, 3 h of test. Finally, it
conversion of methane. An increase in WHSV
is worth to stress that CaO15Ni3 (Fig. 16) has a performance
(0.54 NlCH4 ;in h1 gcat 1 ) implies a slight decrease in methane
similar to CaO30Ni10 (Fig. 17b), probably due to a worse
conversion. At these temperatures, gaseous products
accessibility of Ni in the most CaO loaded sample, caused by
approximately reach thermodynamic equilibrium concentra-
larger amount of calcium carbonate formed during CO2 sorp-
tions (Table 3): an example is given for CaO0Ni3 (Fig. 13a) for
tion in SESMR which increases diffusional resistances.
SMR-procedure1. At 650  C, kinetics is lowered enough to A comparison, for the same Ni-WHSV, between perfor-
better observe the influence of WHSV: when this parameter is mances of CaO15Ni3, CaO30Ni3 and CaO54Ni3 (Table 5) and
equal to 0.24 NlCH4 ;in h1 gcat 1 (Fig. 13a and Table 4), CH4 those of Ni-mayenite catalysts (Table 4, SMR-procedure2 col-
conversion is between 96.7% and 97.8% for all the Ni-WHSV
umn) evidences a detrimental role of CaO on nickel catalytic
values and thermodynamic equilibrium is established; for
activity. The Ni-WHSV of 8.0 NlCH4 ;in h1 gNi 1 represents a
WHSV equal to 0.54 NlCH4 ;in h1 gcat 1 , CH4 conversion de-
good condition for SMR at 650  C on CaO0Ni3 and a very close
creases to 82.2%, and a distance from thermodynamic com-
catalytic activity is observed on CaO15Ni3, but not on
positions is stably recorded (Fig. 14a and Table 3).
CaO30Ni3 or CaO54Ni3. On the other hand, a Ni-WHSV of
With regards to SMR-procedure2, the same qualitative
2.4 NlCH4 ;in h1 gNi 1 is a value low enough to ensure the
considerations can be formulated about influences of WHSV
desired activity on both CaO0Ni10, CaO30Ni10 and CaO54Ni10.
on catalytic performances at 650  C (Figs. 13b and 14b).
In SESMR tests on CaO15Ni3, CaO30Ni10, CaO54Ni10, the
Nevertheless, a comparison with results at 650  C from SMR- lack of a stability in H2 fraction due to sorption enhancing can
procedure1 is interesting: for WHSV equal to be attributed to the chosen ratio between inlet CH4 flow and
0.24 NlCH4 ;in h1 gcat 1 , CH4 conversions obtained by SMR- CaO mass in the packed bed (a comparison can be made with
procedure2 are slightly smaller than those in SMR- results of Cesario et al. [5]).
procedure1, for the same Ni-WHSV (Table 4); this effect is
magnified by a WHSV equal to 0.54 NlCH4 ;in h1 gcat 1 (Fig. 14b).
So, the environment in which SMR is triggered influences
Conclusions
catalyst performance at 650  C: if at this temperature the
catalyst is already surrounded by a produced H2 rich atmo-
NieCaO-mayenite CSCM for SESMR, Ni-mayenite SMR cata-
sphere, it operates better than if must start the reaction from
lysts and CaO-mayenite CO2-sorbents were synthesized in
pure more oxidant reactants (H2O and CH4).
laboratory scale, characterized and experimentally tested.
It is worth to stress here the stability of catalytic activity of A combination of wet mixing and wet impregnation
all tested Ni-mayenite materials, in an overall working time of
methods was applied in laboratory scale for the production of
6 h for each one, summing the time of SMR-procedure1 and
several materials, expected to work as SMR catalysts, CO2-
SMR-procedure2.
sorbent, or both. The wet mixing method effectively produced
mayenite, or CaO-mayenite sorbents with various fractions of
SESMR performed with NieCaO-mayenite free CaO. Subsequent application of wet impregnation
Table 5 summarizes conditions and results of SESMR tests.
method on mayenite and CaO-mayenite let obtain Ni-
 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 2 ( 2 0 1 7 ) 1 3 6 6 1 e1 3 6 8 0 13677

mayenite (a SMR catalyst) and NieCaO-mayenite (a CSCM for

SESMR), respectively, with different Ni loads. Effectiveness of Acknowledgements
these methods was generally proven by XRD spectra of all
synthesized samples, since all desired phases (CaO, The research leading to these results has received funding
Ca12Al14O33, NiO) are present in corresponding samples. from the European Union's Seventh Framework Program
SEM micrographs on as-synthesized powders evidenced ASCENT grand agreement n [608512].
for all samples a granular structure, SEM micrograph on cross
sectional surfaces of embedded samples showed an inhomo- Nomenclature
geneous dispersion of Ni, which is concentrated in external
shells or in internal lodes in all studied samples, and only
Abbreviations
partially dispersed in materials with 10 wt% of Ni. Then, there
BET BrunauereEmmetteTeller
is an influence of Ni fraction on its dispersion on CSCM.
BJH BarretteJoynereHalenda
Influence of CaO load on CSCM properties was investi-
BSE Back Scattering Electron
gated. Materials deriving from CaO-mayenite sorbents with
CSCM Combined Sorbent-Catalyst Material
15 wt% of free CaO had an increase in BET specific surface and
EDS Energy Dispersive X-ray Spectroscopy
BJH specific pore volume after wet impregnation procedure.
FWMH Full Width at Medium Height
Moreover, strong interactions with Ni are evidenced by their
GC Gas Chromatograph
main reduction peaks during TPR, located at temperatures
JCPDS Joint Committee on Powder Diffraction Standards
higher than 800  C. On the other hand, CSCM deriving from
Ni-WHSV Nickel Weight Hourly Space Velocity
CaO-mayenite sorbents with 30 wt% of free CaO or more un-
SEM Scanning Electron Microscopy
derwent a slight decrease in the same pore properties after
SESMR Sorption Enhanced Steam Methane Reforming
wet impregnation, and had weaker interactions with Ni, since
SMR Steam Methane Reforming
their main reduction peaks occur at temperature below 750  C.
TCD Thermal Conductibility Detector
Concerning to CO2-capture properties, sorption/regenera-
TGA Thermo-Gravimetric Analysis
tion multicycles in TGA underlined the general tendency to
TPD Temperature Programmed Desorption
the stabilization of sorption capacity with cycle number in-
TPR Temperature Programmed Reduction
crease after the 20th, with regeneration under inert atmo-
WHSV Weight Hourly Space Velocity
sphere, for both CSCM and their CaO-mayenite parent
XRD X-Ray Diffraction
sorbents. This can be attributed to the role of mayenite as an
inert binder for CaO, limiting its sintering. Moreover, each Symbols
CSCM globally had a lower sorption capacity than its CaO- c volumetric concentration on dry and free diluent
mayenite parent sorbent during the whole 50 cycles, prob- basis, vol% on dry and free diluent basis
ably because of wet impregnation, which can give a partial cGC actual volumetric concentration measured by GC,
CaO removal from the parent sorbent, and because of shad- vol% on dry basis
owing effect of nickel-calcium-aluminum shells. F molar flowrate, Nl/h
CaO load had high influences in reforming performances K Scherrer equation constant, #
too. In fact, Ni-mayenite materials and CSCM with the same L average crystallite size, nm
Ni load have different catalytic performances with the same m packed bed mass, g
experimental conditions (WHSV ¼ 0.24 NlCH4 ;in h1 gcat 1 , at- wNi nominal nickel weight fraction in packed bed, wt%
mospheric pressure, inlet steam to carbon molar ratio ¼ 3,
650  C). Ni-mayenite catalysts always got SMR equilibrium Greek letters
fractions in product gases, with a stable CH4 conversion, 2q Bragg angle, degrees
independently on their Ni load (from 10 wt% to 3 wt%). For l radiation wavelength, Å
CSCM deriving from sorbent with 15 wt% of free CaO, 3 wt% of c conversion, %
Ni gave rise to a good and stable catalytic performance, with
SESMR occurring in the first part and SMR proceeding after Subscripts
sorbent saturation. On the contrary, with CSCM coming from i gaseous component (N2, CH4, H2, CO, CO2)
sorbents with 30 wt% and 54 wt% of free CaO, a 3 wt% of Ni in inlet
was not enough to maintain a stable CH4 conversion during j gaseous component (CH4, H2, CO, CO2)
the test, so neither a sorption enhancing effect nor a satis- Ni nickel
factory reforming activity could be achieved. An increase up to Out outlet
10 wt% of Ni, on the same kind of sorbents, was necessary to
reach these goals. Also the behavior during catalytic tests
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