Chemical Engineering Journal 264 (2015) 697705

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Chemical Engineering Journal

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Performance of a combined CaO-based sorbent and catalyst on H2

production, via sorption enhanced methane steam reforming
Ana L. Garca-Lario , Gemma S. Grasa, Ramn Murillo
Instituto de Carboqumica, (CSIC), Miguel Luesma Castn 4, 50018 Zaragoza, Spain

h i g h l i g h t s

 A hybrid CO2 sorbent and reforming catalyst was synthesized through physical mixing.
 It presents a CO2 carrying capacity over 20 wt.% with respect the CaO in the solid.
 H2 percentages close to equilibrium are achieved even for a steam to carbon ratio as low as 1.5.
 It was tested cyclically under realistic conditions with H2 yields over 90 vol.%

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

Article history: The performance of an hybrid material CO2-sorbent and reforming catalyst under Sorption Enhanced
Received 15 September 2014 Reforming of methane has been assessed. The material was synthesised through physical mixing of
Received in revised form 18 November 2014 CaO, NiO and calcium cement aluminate (varying the proportion CaO/NiO to produce three different
Accepted 23 November 2014
solids). The materials, that presented a stable CO2 carrying capacity of 20 wt.% of the total CaO in the solid,
Available online 29 November 2014
were able to reach gas product composition very close to thermodynamical equilibrium (at 650 C, steam to
carbon ratio, S/C, of 3 and 1200 h 1 CH4 spatial velocity), with H2 composition over 94 vol.% (dry basis). In
Keywords:
addition, it has also been demonstrated that the hybrid materials with NiO wt.% contents of 14 and 18.5 can
H2 production
CO2 capture
fulll the thermodinamical equilibrium at S/C ratios as low as 1.5. Finally the 18.5% NiO material has been
Sorption Enhanced Reforming tested in cyclic operation, under realistic conditions by regenerating the sorbent in oxidizing conditions. The
Multifunctional catalyst cycled material showed slight increase of NiO crystal size that resulted in slight loose of activity after
cycling. However, H2 percentages over 90 vol.% (dry basis) were always obtained.
2014 Elsevier B.V. All rights reserved.

1. Introduction 1530 bar and shift reaction is conducted in secondary reactors

Hydrogen is a raw material used in several industrial processes
as ammonia and methanol synthesis, hydro cracking and hydro
processing in reneries, hydrogenation of ethylene, metallurgical
processes or glass production. Its demand is expected to increase
once the recent proposed applications as low-emission fuel (for
gas turbines and combustion engines i.e.) become a proven alter-
native as energy conversion systems for electricity production
[1]. Around 50% of the H2 produced worldwide present a fossil fuel
origin as it is produced via Steam Methane Reforming (SMR) [1,2].
This is an energy intensive process performed in several steps at
severe conditions regarding to operating pressure and temperature
(reforming of methane with steam takes place at 800900 C and
Corresponding author. Tel.: +34 976 733977.
E-mail addresses: algarcia@icb.csic.es (A.L. Garca-Lario),
(G.S. Grasa), ramon.murillo@csic.es (R. Murillo).
at a lower temperature around 200400 C). Moreover, it is
reported that around 8 ton CO2 per ton H2 produced via Steam
Methane Reforming are emitted [3]. In this context, large scale
hydrogen production processes including CO2 capture at a reduced
cost and more efciently than existing processes, constitute a great
challenge in the climate change mitigation route [47].
As an alternative to the SMR, the Sorption Enhanced Reforming
(SER) process proposes the addition of a Ca-based CO2 acceptor to
the commercial SMR catalyst so that the reforming, shift and CO2
removal processes take place simultaneously in the reactor [8].
The combination of chemical and separation reactions simplies
the process, improves efciency and enhances conversion and
hydrogen yield. According to SER equilibrium (whose reactions
are shown in Fig. 1), product gas with a H2 content around 96 v.%
dry basis (d.b.) is possible in a wide range of temperatures from
650 to 750 C when using CaO-based sorbents in a single reaction
gga@icb.csic.es step [812]. Several congurations have been proposed for the pro-
cess. One of the preferred congurations for scaling up, proposes

http://dx.doi.org/10.1016/j.cej.2014.11.116
1385-8947/ 2014 Elsevier B.V. All rights reserved.
698 A.L. Garca-Lario et al. / Chemical Engineering Journal 264 (2015) 697705
the use of two interconnected uidized beds operating at atmo-
spheric pressure [8,13]. In this way, the reformer/carbonator reac-
tor would operate at around 650 C, and the gas stream exiting this
reactor would be mainly comprised by H2, steam and low content
of unconverted CH4, CO and CO2. To operate the process cyclically,
it is required a regeneration step, and a common method to supply
the energy required to calcine the sorbent in the calciner reactor is
the oxy-combustion of a gas fuel operating at temperatures close
to 900 C [1416]. The scheme of this process is shown in Fig. 1.
An important operation parameter in the process conguration
depicted above, besides reforming temperature and pressure, is the
steam to carbon ratio (S/C) in the reformer. The S/C ratio has a
great inuence over product gas composition and, according to
equilibrium, high S/C ratios in reforming processes improve
methane conversion, promote the CO2 production and decrease
CO selectivity due to the reverse water gas shift reaction that is
equilibrium limited. In SER, the trend for the gas composition is
similar to that shown in SMR but thanks to the reaction of CO2 with
CaO, the changes of CO2 concentration are less abrupt at different
steam to methane ratios [8,9]. However, from the perspective of
the global performance of the H2 production plant in terms of
equivalent H2 efciency and CO2 emissions, a compromise
between H2 purity, CH4 conversion in the reformer and energy
efciency of the global process should be reached. In this way,
low S/C ratios would be preferable in a self sustained SER plant
for H2 production where the steam needs in the reformer are
generated thanks to the integration of the high temperature energy
exceeding sources of the process within a steam cycle; and the
energy required in the calciner to regenerate the sorbent is
provided by the oxy-combustion of the off gas of a PSA unit that
puries the H2 rich gas obtained in the reformer unit [16,17].
A critical issue for the development of the SER process is the
availability of materials able to sustain the reactions involved in
the process, these materials are: the catalyst and the CO2 acceptor
sorbent. Regarding to the catalyst selection, it is required that it
presents high catalytic activity at a range of temperatures lower
than typical temperatures for SMR and it must prove its stability
along multiple oxidation/reduction periods as the regeneration in
the calciner will take place in an oxidant environment. Finally its
reduction kinetics in presence of steam and at low temperature
must be reasonable [18]. Traditionally, Ni acting as active phase
supported on diverse inert materials has been used in methane
reforming because it presents a high activity and it is more eco-
nomical than other precious metals [3,19]. Several materials such
as a-Al2O3, that is commonly used in SMR due to its stability at
high temperatures and its low price, have been proposed as inert
Fig. 1. Simplied Sorption Enhanced Reforming process (SER) scheme.
support [3,20]. However, the possible formation of NiAl2O4 that
is not easily reducible at low temperatures and it is produced by
NiO and Al2O3 reaction during the calcination stage, impulse the
search for alternative catalysts and supports [2124]. For example,
a NiO/NiAl2O4 catalyst that has been proved to be able to reach gas
compositions close to equilibrium in CH4 reforming experiments
after being submitted to oxidation/reduction cycles [21]. Other
supports that contain alkaline metals as Mg [2527] have been
proposed to operate even at lower temperatures than 500 C, and
a NiO/CaAl4O7 catalyst, whose stability in oxidation/reduction
cycles has been also assessed, has been proposed as a reforming
catalyst for SER [18].
Concerning to the sorbent selection, its preferred characteristics
are a sufcient CO2 carrying capacity stable with the number of
carbonation/calcination cycles; durability comparable to the
catalysts, to minimize the requirements of purge of the system to
renew the spent sorbent; and adequate kinetics for CO2 capture
and regeneration. From a thermodynamical point of view,
CaO-based sorbents are in principle one of the most suitable CO2
acceptors as they present a good ability to react with CO2 at low
partial pressures at moderate temperature and also present fast
kinetics [8,14]. Therefore, there is an important amount of works
in the literature using natural CaO-based sorbents (limestone or
dolomite) on SER, [9,12,25,28,29] as reviewed by Harrison [8].
However their well-known decay of CO2 capture capacity with
the number of reaction cycles [3032] led to an intense work on
the development of Ca-based synthetic sorbents [8,33]. In particu-
lar, sorbents synthesized doped with Al present a high stability
after several carbonation/calcination cycles due to the formation
of stable mixed metal oxide compounds as for example mayenite,
Ca12Al14O33, that provides a stable framework between the CaO
particles and reduces the sintering of active CaO [3440]. As
reviewed by Li et al. [40] the calcium precursor has an important
effect on its reactivity, and the utilization of CaO precursors sinter-
ing resistant, or nano-scale CaO showed promising results. Differ-
ent routes have been reported in the literature to incorporate the
inert support on CaO particles, [33,40] being the most common
methods the sol-gel combustion synthesis, [3436] sol mixing
(one soluble powder with one insoluble powder), [37] and mixing,
calcining and pelletization [38]. Following this last method
Manovic and Anthony, with the objective to produce an stable
CaO-based sorbent, and also attractive from the economical and
production point of view, prepared a CaO/Ca12Al14O33 sorbent by
physical mixture of natural CaO and calcium aluminate cement
as binder obtaining an efcient porous solid that presented
satisfactory performance in long multicycle testing [41].
 A.L. Garca-Lario et al. / Chemical Engineering Journal 264 (2015) 697705
Recently, with the objective to reduce the amount of inert
material in the SER Ca-looping system that would decrease the vol-
ume of the reactors, and also would affect positively to the energy
balance of the process, the works that aim the use of a single par-
ticle that contains both CaO sorbent and reforming catalyst have
increased [4245]. The concept of the hybrid material could be
as shown in Fig. 2, and the intimate contact of catalyst and sorbent
in the solid could also improve the kinetics of the SER process.
Satrio et al. designed spherical core-shell pellets that consisted
of a natural sorbent (lime or dolomite) enclosed in an alumina shell
that was loaded with Ni via impregnation methods [42,46]. These
materials that contained around 10 wt.% CaO and 6 wt.% Ni were
tested satisfactorily in a xed bed reactor with H2 in the gas stream
reaching the equilibrium composition [47]. However the cyclic
testing of the materials showed the typical loose in carrying
capacity of the natural CO2 sorbent core. Moreover the ratio
inert/sorbent/catalyst would not allow for a full-scale design of
the process. Martavaltzi and Lemonidou eliminated the alumina
support and designed a multifunctional material formed by
NiOCaOCa12Al14O33 where the proportion CaO/NiO is a key
parameter on the H2 content in the product gas [43]. They showed
that 16 wt.% NiCaOCa12Al14O33 was able to produce a gas stream
containing 90 vol.% H2 (d.b.) at 700 C, S/C ratio 3.4 and around 500
CH4 h 1 spatial velocity. However, although the material acted as
an efcient CO2 sorbent under SER conditions, its functionality as
catalyst was limited, resulting in a slightly lower CH4 conversion
than equilibrium predictions. Chanburanasiri et al. also produced
all in one solids, but in this case through incipient wetness tech-
nique using natural CaO and hydrotalcite (MK30-K) as both, sup-
port and CO2 sorbent [44]. They tested different NiO loads in
xed bed reactor at a steam to methane ratio of 3. The conclusions
of their study conrmed that CaO is a good support for Nickel cat-
alyst what eliminates the use of traditional support thereby mini-
mizing the size of reactor. Nevertheless although the catalytic
activity of NiO/CaO solid was less than NiO/Al2O3 catalyst, the
hydrogen concentration at exhaust gases was relatively high
(80 vol.% db) at 600 C and a CH4 spatial velocity of around
600 h 1. Jong-Nam Kim et al. prepared a NiOCaOCa12Al14O33
combining a precipitation and hydration technique [45]. Again,
the formation of Ca12Al14O33 provided stability at the solid as it
was reported by this group. They also reported good performance
of their material under SER conditions, comparable to the physical
mixture of separate solids (catalyst and sorbent). Solid with 7 wt.%
Ni showed good behavior at a CH4 spatial velocity of around
1200 h 1, and reached hydrogen concentrations of 95 vol.% (d.b.)
in the exhaust gas and good repeatability was achieved after 4
cycles for this hybrid material.
Physical mixing has been also proposed as a valid method to
prepare hybrid materials, using calcium aluminate cement as a
binder to produce CuOCaO pellets following a similar procedure
as for the synthetic sorbents [38,48,49].
Following the physical mixing route, the objective of the
present work is to synthesize a new hybrid material containing
both the CaO-based CO2 sorbent and the reforming catalyst, using
Fig. 2. Conceptual representation of an hybrid sorbent-catalyst material.
699
calcium aluminate cement as a binder and source of mayenite. The
stability of the solids in terms of CO2 carrying capacity has been
determined in multicycle carbonation/calcination tests. The func-
tionality of these solids under SER conditions as a function of their
composition in terms of NiO load and CaO content has been satis-
factorily proved. To achieve this objective, the materials have been
tested in a micro-reactor under SER conditions, and the effect of
S/C ratio on gas composition has been evaluated. The best material
has been submitted to consecutive reforming/carbonation and oxi-
dation/calcination cycles to determine the suitability of the mate-
rials synthesized in continuous cyclic operation.
2. Experimental
CaO derived from the calcination of natural limestone (2 h, at
900 C, >95% CaO in the calcined material), and powdered NiO
(99.99% Sigma Aldrich) were the starting materials for the hybrid
solid, that was prepared by physical mixing. Three materials were
prepared varying the proportion of CaO/NiO. In all of them, a
10 wt.% of calcium aluminate cement (Electroland) with respect
to the CaO content was added. The calcium aluminate cement
acted as a binder and a source of Ca12Al14O33 after calcination of
the solids, in a similar way as the description given by Manovic
et al [41]. The three powdered solids were mixed in a baker with
water. The resulting mixture was air-dried for 24 h. Finally, the
samples were crushed and sieved (200400 lm).
The solids have been named according to their relative weight
percentage of NiO, this is: 18.5NiO (18.5 wt.% NiO, and 74 wt.%
CaO); 14NiO (14 wt.% NiO, with a 78.5 wt.% CaO) and 9NiO
(9 wt.% NiO, with a 82 wt.% CaO).
The materials have been texturally, physically and chemically
characterized in their calcined form (at 800 C in air). The so called
fresh solids were directly calcined after preparation and then
characterized. The used solids were calcined after being submit-
ted to SER process. The BET surface areas were determined in a
Micromeritics ASAP-2020 by nitrogen adsorption at 196 C. The
density of the solids has been determined by means of a pycnometer
AccuPyc II 1340 while Mercury Porosimeter has been applied to
determine pore volume with a Quantachrome Pore Master. XRD
analysis were conducted in an X-ray diffractometer Bruker
D8Advance, using the Cu Ka radiation, to dene the crystalline
structure and the crystallite size of the solids prepared. Hitachi
S-3400 N scanning electron microscopy (SEM) was used to observe
the morphologies of the prepared solids (surface morphology and
cross-section), the metal distribution was evaluated using energy
dispersive X-ray (EDX) analysis. Temperature programmed reduc-
tion (TPR) of the fresh materials were carried out in order to deter-
mine the reduction temperature of the reducible phases in the
solid. The TPR analysis was done in a Micromeritics PulseChemi-
sorb 2700 apparatus heating the sample at 20 C/min from room
temperature to 950 C in 10% H2 in Ar.
The CO2 carrying capacity of the hybrid materials was assessed
in an atmospheric TGA apparatus able to operate cyclically. The
TGA apparatus consisted of a quartz tube reactor with a platinum
basket suspended from it, inside a two-zone furnace. The furnace
can be moved up and down by means of a pneumatic piston, and
the position of the furnace with respect to the platinum bas-
ket allowed the alternation between calcination and carbonation
conditions. The temperature and sample weight were continuously
recorded on a computer and the reacting gas mixture was regu-
lated by mass ow controllers and fed in through the bottom of
the quartz tube. Steam was generated by external electric heating
of the water ow controlled by a liquid mass ow controller and
then introduced into the reaction atmosphere for some specic
tests. Around 5 mg of hybrid material were placed in the platinum
700 A.L. Garca-Lario et al. / Chemical Engineering Journal 264 (2015) 697705
basket on every test that consisted of 100 reaction cycles. The
experimental routine consisted on the calcination of the material
at 900 C in a 70 vol.% CO2 in air for 7 min., and the carbonation
of the solid was carried out at 650 C in a 15 vol.% CO2 in air for
5 min. Also, some specic samples have been submitted to calcina-
tion/carbonation tests that included a 15 vol.% of steam during the
carbonation stage.
The catalytic activity of the hybrid material, as well as its per-
formance under SER conditions, were determined in a xed bed
reactor system described in detail by Garcia-Lario et al. [21] The
reactor is a quartz tube, 4 mm of inner diameter, electrically heated
by a cylindrical oven. Two thermocouples measure and control the
bed temperature. Around 500 mg of the solid sample was intro-
duced in the reactor on each test that resulted in around 40 mm
of bed height. CH4, N2 and water were feeding into the system by
mass ow controllers being the water previously evaporated at
200 C. Once the exhaust steam is condensed, the gas products
were analyzed by a gas chromatograph (Varian CP-3800). All the
experiments were conducted under atmospheric pressure at
650 C. Previously to the reforming test, the solids were reduced
at 650 C in a ow of 30 vol.% H2/N2 for 1 h.
The experiments carried out, whose CH4 spatial velocity and S/C
ratios are compiled in Table 1, served to assess the performance of
the hybrid material with respect to H2 production via SER, and also
to evaluate the catalytic activity of the solids once the sorbent part
of the material has been saturated (SMR). Finally, one of the hybrid
materials that fullled equilibrium compositions, was selected to
carry out a multi cyclic test (7 cycles in total) where the solid
was alternatively submitted to SER conditions (at 650 C, S/C 3
and 550 h 1 CH4) to regeneration conditions carried out at 875 C
in air. An intermediate stage of pre-reduction at 650 C and
10 v.% H2 was carried out between every calcination and SER stage.
The experimental results were compared to the equilibrium
predictions obtained by means of the process simulator Aspen
Hysys at similar experimental conditions.
3. Results and discussion
The BET surface area of the fresh materials synthesized along
with XRD results (crystalline phase and NiO particle size) are sum-
marized in Table 2. As it is expected, the BET surface area of the sol-
ids is slightly lower than the BET surface area of the calcined
limestone (15 m2/g), however the differences are not signicant.
The data are consistent with BET areas of hybrid solids reported
in the literature prepared through mixing, as for example, the
9 m2/g BET surface reported for solids that contained 25 wt.%
NiO, by Martavaltzi et al. [43]. And, they are even higher than those
prepared through impregnation, as for example Chanburanasari
et al. who obtained a BET area of 4 m2/g for a 12.5 wt.% Ni load
[44]. According to the experimental results, the BET area does
not follow a signicant diminishing trend when the Ni content is
increased, in contrast with data reported in the literature [43].
The crystalline phases of fresh materials obtained by XRD anal-
ysis denote that no mixed phases are found. This indicates that CaO
and NiO do not interact, and although nickel might react to form
NiAl2O4, the presence of CaO avoids this reaction [50,51]. There-
fore, only CaO and NiO were detected along with small amount
Table 1
Experimental conditions for the SER and SMR experiments.
1
wt.% NiO CH4 (h ) SER SMR Comment
9 1200 S/C = 3 S/C = 3
14 1200 S/C = 3, 1.5 S/C = 3, 1.5
18.5 1200 S/C = 3, 1.5 S/C = 3, 1.5
18.5 550 S/C = 3 S/C = 3 7 cycles
of Ca12Al14O33 due to the addition of cement aluminates, in concor-
dance with results published in the literature [38] and a negligible
amount of Ca(OH)2 that was formed after the calcination due to the
atmospheric moisture. Regarding to the NiO crystallite size, that
depends on several parameters such as nickel amount, catalyst
support, and preparation method or reduction process [52,53]
and that will affect the catalyst activity and resistance to coke
deposition [52], its average value is in concordance to other hybrid
solids reported in the literature (for example, 37.7 nm for 25 wt.%
NiO hybrid materials prepared by Martavaltzi et al. [43]) and no
relation was found between the nickel load and NiO particle size.
However, as it was expected, a small increment in NiO crystal size
was found after the solid was cycled between reduction environ-
ment to oxidant conditions during the sorbent regeneration stage
(see Tables 2 and 3 for comparison).
The results from TPR for the three fresh solids with different
NiO content showed a single peak at about 400 C with a hump
nearly 500 C that corresponds to free NiO [53,54]. It was not iden-
tied a hump at higher temperatures that would have indicated
that part of the NiO could be buried in the CaO structure [50].
These results are in agreement with XRD patterns which showed
that the only reducible phase in the hybrid material was NiO.
Table 3 shows the characterization of the so called 18.5NiO
solid after one reaction cycle (including SER stage and calcination
stages) and after ve reaction cycles. According to XRD analysis,
besides CaO and NiO, the presence of Ca12Al14O33 was also con-
rmed. As it can be seen BET surface area does not suffer an impor-
tant decrease with the number of reaction cycles and similar
results have been found with respect solid porosity that is around
50% after 5 reaction cycles. The density of the solid decreases
slightly as long as the number of reaction cycles increases and in
spite of the NiO crystal size that slightly increases with the number
of the cycles as is expected, there are no signals of important sin-
tering phenomena. This has been corroborated through SEM anal-
ysis of the supercial and cross section of the solids, some pictures
corresponding to the 18.5NiO material have been included as
examples in Fig. 3. The surface image of the fresh material shows
a good nickel distribution (Fig. 3a), but the cross section proofs
three different morphological phases (Fig. 3b): phase 1 rich in Ca,
phase 2 rich in Ni and phase 3 mixture of Ca and Ni. Al presence
was determined in all particles. The formation of different phases
in hybrid solids has been also detected by other authors [43]
and, the different phase distribution is an expected result due to
the low CaNi interaction [53,55]. Slight sintering was found on
supercial images (Fig. 3c) of the cycled material. Its cross section
pictures revealed a porous material with the nickel inside the par-
ticle being accessible to the reacting gas through the channels
along the particle (Fig. 3d).
To determine the effect that the NiO content has on the CO2 car-
rying capacity of the hybrid solids, the materials have been submit-
ted to calcination/carbonation cycles that include a demanding
calcination stage carried out at high temperature and in a concen-
trated CO2 stream (900 C and 70 v.% CO2), and a short carbonation
time (at 650 C, 15 v.% CO2 for 5 min). The results shown in Fig. 4a
are represented in terms of mass fraction conversion referred to
the total CaO present in the solid material, although part of it will
be in the mayenite formed after the rst calcination. The results
obtained have been compared with the CO2 carrying capacity that
presents the parent limestone source of CaO for the hybrid materi-
als. As it can be seen in Fig. 4a, the materials still present the typ-
ical decay in sorption capacity with the number of calcination/
carbonation cycles that has been widely described in the literature
as typical from natural CaO-based sorbent [8,30,31]. However,
after the initial rapid decay, the CO2 carrying capacity of the solids
tends to stabilize and remains at 12 wt.% with respect to the total
mass of CaO in the solid after 100 cycles (9 wt.% with respect to
 A.L. Garca-Lario et al. / Chemical Engineering Journal 264 (2015) 697705 701

Table 2
Fresh materials characterization.

Solid NiO (wt.%) SBET (m2 g 1

) NiO dp (nm) Crystalline phase
9 12 1.7 36 NiO, CaO, Ca12Al14O33a, Ca(OH)2a
Fresh 14 13 1.8 38 NiO, CaO, Ca12Al14O33a, Ca(OH)2a
18.5 14 1.9 26 NiO, CaO, Ca12Al14O33a, Ca(OH)2a
a
Lesser extent.

Table 3
Characterization of 18.5NiO after reaction cycles.

Solid e (%) SBET (m2 g 1

) q (g/cm3) NiO (dp) nm Crystalline phase
1st cycle 51.6 17.1 3.2 38.5 NiO, CaO, Ca12Al14O33
5th cycle 50.3 13.2 2.6 39.5 NiO, CaO, Ca12Al14O33

Surface Cross-section hybrid material did not have important inuence on the stability,
or the CO2 carrying capacity of the materials. This is in line with
(a) (b) the results presented by Martavaltzi and Lemonidou [43] that
found an optimum for a material with a 20 wt.% NiO, but with
minor differences among the materials that they developed (NiO
contents varied from 10 to 25 wt.%). On view of these results, the
Fresh 18.5NiO material was selected for an additional calcination/car-
bonation test that included steam in the carbonation reaction
atmosphere (15 vol.% steam, 15 vol.% CO2 in air, 650 C and 5 min
reaction time). Fig. 4b shows how in these conditions, that could
be representative of a SER process operated in continuous mode
(c) (d) in a dual uidized bed system. The residual capacity of the material
is stabilized around 20 wt.% with respect to the total CaO in the
solid (15 wt.% with respect to the total mass of the hybrid mate-
5 rial). Although it is not possible to compare directly the CO2 carry-
ing capacity of the materials tested with results published in the
Cycle literature, as carbonation conditions in terms of carbonation time
and/or [5658] CO2 partial pressure [59] and also the calcination
conditions have a very important impact on sorbent CO2 residual
carrying capacity, it is important to highlight the stability of the
Fig. 3. SEM surface and cross-section images of the 18.5NiO material, fresh and
materials tested at a high number of cycles that is in agreement
used after 5th cycle.
with the results reported by solid sorbents prepared by physical
mixing [37,38,43,60], and also by sorbents prepared by precipita-
the total mass of the hybrid material). As it can be seen the carry- tion and hydration [45].
ing capacity of the synthetic solids is highly stable after around 20 To evaluate the performance of the synthesized solids as func-
reaction cycles, and it almost doubles the capacity of the natural tion of their NiO content with respect to the SER process, and also
lime. It suggests that the Ca12Al14O33 formed contributes to main- their catalytic activity in SMR (once the active CaO in the solid has
tain the porous structure of the material, in line with the results reacted to form CaCO3 and the reaction takes place only thanks to
from Hg porosimetry and the BET surface area that do not dimin- the catalytic part of the solid), several reforming tests have been
ishes signicantly after 5 reaction cycles. The NiO content in the carried out, whose experimental conditions are compiled in Table 1.

Fig. 4. (a) Evolution of CO2 carrying capacity, expressed in wt.% CaO conversion, of the hybrid materials and natural CaO source. Calcination 900 C, 70 vol.% CO2 in air,
carbonation at 650 C, 15 vol.% CO2 in air. (b) Evolution of CO2 carrying capacity of the 18.5NiO material. Calcination under identical conditions as in gure (a), carbonation
carried out at 650 C, 15 vol.% CO2, 15 vol.% H2O in air.
702 A.L. Garca-Lario et al. / Chemical Engineering Journal 264 (2015) 697705
In rst place, the effect of the material NiO content, on product gas
composition at 650 C, CH4 space velocity of 1200 h 1 and for a
given steam to carbon ratio of 3 has been assessed.
Fig. 5 shows an example of the experimental results obtained in
the micro xed-bed reactor, in terms of evolution of the product
gas composition with time for the 18.5NiO material. In this gure,
the continuous lines represent the experimental data, the long
dash lines symbolize SER equilibrium according to Hysys calculus
referred to experimental conditions, and dotted lines indicate the
SMR equilibrium also according to Hysys calculations. As it can
be seen in Fig. 5, the experimental curves present the three typical
stages widely described in the literature for SER experiments (see
for example the review by Harrison) [8,9,12]. These are: the pre-
breakthrough period (where reforming, shift and carbonation reac-
tions take place at the same time), breakthrough (the sorbent starts
to be saturated and CO2 removal starts to decrease until the sor-
bent is totally saturated) and post-breakthrough (the sorbent is
saturated so CO2 sorption is no longer effective and only Steam
Methane Reforming takes place). As it can be seen in Fig. 5, in this
experiment H2 concentration reaches the 94 vol.% (d.b.), in close
agreement with the equilibrium predictions. This composition is
typical of a pre-break-through period where the CaO is reacting
with CO2 and shifting the equilibriums toward H2 production.
Low concentration of CO, CO2 and CH4 are measured during this
period. CH4 conversion is approximately 98% and the productivity
performance is around 0.15 kgH2/kghybrid solid
hour. These values
are consistent with data of hybrid solids reported in literature. As
instance Kim et al. [45] get a gas composition close to equilibrium
concentration values reaching a productivity performance of
around 0.13 kgH2/kghybrid solid hour while Martavaltzi et all [43]
achieve a productivity performance of around 0.041 kgH2/kghybrid
solid
hour and also a lower methane conversion was obtained
(around 80%). After this initial stage, H2 concentration follows a
gradual drop until it is stabilized in the so called post-break-
through period at around 80 vol.% (d.b.), while CO2 concentration
increases up to 11 vol.% At this point, the carbonation is not effec-
tive as the sorbent part of the hybrid solid is saturated (similar
trend to CO2 is followed by CO as expected) and gas composition
corresponds to that predicted by the SMR equilibrium. The gas
composition remains stable, and the catalytic part of the hybrid
material is able to maintain its reforming activity. Similar experi-
mental curves (with the three reaction periods) are obtained for
the 14NiO and the 9NiO hybrid materials at a ratio S/C = 3 and a
space velocity of 1200 h 1 CH4. Fig. 6 resumes the experimental
results in terms of H2 vol.% concentration in d.b., for the pre-break-
through period (SER conditions) and the post-breakthrough (SMR
Fig. 5. Evolution of gas composition with time for the experiment carried out with
the 18.5NiO material, at 650 C, S/C = 3 and 1200 h 1 CH4 spatial velocity.
conditions). The experimental values are compared with the equi-
librium predictions. It can be seen that the 14NiO material fullls
the equilibrium predictions producing a 93.5 vol.% H2 d.b. gas
product, and presenting a CH4 conversion around 98%. The mate-
rial with the lower metal load (9NiO material), presented a CH4
conversion around 75%, that resulted in a 90 vol.% H2 (d.b.) in the
gas product stream, that is slightly lower than equilibrium predic-
tions. The activity of the 9NiO material once the sorbent part has
been saturated is also limited, and the H2 concentration in the
gas stream in the so called post-breakthrough period is sensibly
lower than that predicted by the equilibrium (65 v.% H2 d.b. with
respect to the 76 v.% d.b. predicted by the equilibrium) and does
not remain stable in the experiment. It is clear that there is a min-
imum amount of NiO required in the solid to maintain its activity
either in SER or SMR. This result is in line with studies compiled in
the literature, where lower CH4 conversion at lower Ni loads was
also found for other authors in hybrid solids prepared by different
synthesis routes. For example, Martavaltzi and Lemonidou [43]
found that increasing the nickel load in the solid leads to increased
the conversion at both pre-breakthrough and post-breakthrough,
reaching a maximum peak when the NiO content in the solid
was 20 wt.%, at 650 C and S/C = 3.4. Under these conditions, they
obtained a 90 vol.% H2 gas stream, which is slightly below equilib-
rium predictions. Chanburanasiri et al. [44] prepared hybrid solids
by incipient wetness technique and studied at 600 C and S/C = 3
the effect of changes in nickel loads over the solid. These authors
also found that it is necessary a minimum load on nickel in the
hybrid solid to be active enough as reforming catalyst. Radfarnia
and Illuta [61], varied the NiO content in their materials between
12 and 25 NiO wt.% in their solids, being the material with the
highest load the material that had better performance. Kim et al.
[45] synthesized solids with a Ni content between 3 and 10 wt.%,
reaching the best performance close to equilibrium predictions
(at 650 C, S/C 3.1, 1000 h 1 CH4) with a 7 wt.% Ni material.
Once the 9NiO has been discarded due to its slightly low perfor-
mance at the most favorable reaction conditions tested in this
work, the behavior of the 14NiO and 18.5NiO materials at a lower
S/C ratio = 1.5 (at 650 C and 1200 h 1 CH4) under SER conditions
has been evaluated. The results in terms of H production, that
are compiled in Fig. 6, show that the gas composition in both
experiments fullls the equilibrium predictions for the pre-break-
through period achieving both solids a gas product with around
84 vol.%. H2 (d.b.) while methane conversion values for this exper-
iments (66% and 69.6% respectively) that are close to the predicted
by the equilibrium (72%). Once the sorbent part of the solid is in
form of CaCO3 and the capture of CO2 is not longer efcient, the
14NiO and 18.5NiO materials behave different. Although the
18.5NiO is able to reach the reforming equilibrium for the SMR
with a H2 production of 71 vol.% on d.b., the gas composition pro-
duced by the 14NiO material is well below the equilibrium predic-
tions with only a 61 vol.% H2 in the product gas stream. It is well
known that CO2 removal makes possible to use less active catalyst
[11] as the carbonation reaction shifts the equilibriums toward H2
formation, improving the performance of the catalyst promoting
its activity at SER step at less favorable conditions for the catalyst
(lower steam to methane ratio).
The possibility to work at a very low steam to methane ratio
(S/C = 1.5) at usual nickel content (1418.5 wt.% NiO) is a novel,
and a very interesting result for hybrid materials, as the results
reported in the literature comprise experimental conditions with
S/C ratios between 3 and 5 [43,45,61]. A material able to operate
satisfactorily at this low S/C ratio would allow minimizing the
energy penalty of the process that is mainly associated to the
steam consumption either in the reformer, or in the calciner. Also,
a sorbent-catalyst able to work at such as low S/C values would
allow for the design of an energy self-sustained SER plant where
 A.L. Garca-Lario et al. / Chemical Engineering Journal 264 (2015) 697705
Fig. 6. H2 gas product content in d.b. under Sorption Enhanced Reforming conditions (SER), and Steam Methane Reforming (SMR), for the experiments carried out with the 9,
14, 18.5NiO materials and at S/C ratios of 1.5 and 3. Reaction temperature 650 C, and 1200 h 1 CH4. Discontinuous lines represent equilibrium composition.
the off-gas from the H2 purication unit is used to provide the
energy necessary in the calciner reactor [16,17].
With respect to the solids performance once the sorbent part of
the hybrid material is no longer active for CO2 capture, as it can be
seen also in Fig. 6, the amount of Ni is critical for the activity of the
catalyst. As it has been conrmed experimentally, high S/C favors
the reforming reaction for both the SER and SMR conditions. In this
way, for an S/C = 3, equilibrium compositions are achieved with the
18.5NiO regardless the activity of the sorbent part of the solid.
When reducing the ratio S/C down to 1.5, it can be seen that the
18.5NiO hybrid material is able to produce a gas stream that fullls
the thermodynamical equilibrium at the SMR conditions maintain-
ing the steady state for more than one hour. It has been experimen-
tally observed that catalyst deactivation depends strongly on the
NiO load of the solid for different S/C values. While the 18.5NiO
solid is able to act not only as SER catalyst but also as a SMR cata-
lyst at an S/C as low as 1.5, the 14.5NiO material does not achieve
equilibrium compositions for S/C = 3 and lower S/C rates, being the
catalyst part of the solid not able to convert CH4 as would be
marked by the thermodynamics. However, as described above,
the presence of active CaO during the SER period is able to push
up the activity of the hybrid material and the H2 composition at
S/C = 1.5 corresponds to that predicted by the thermodynamics
for 14.5NiO solid.
Finally once it has been proved the suitable performance of the
hybrid materials synthesised with respect to H2 production in a
SER process, a cyclic experiment has been carried out with the
18.5NiO solid. The experiment comprised a SER stage at 550 h 1
CH4, at S/C = 3 and 650 C. Once the sorbent was saturated the sta-
bility of the material under SMR was also evaluated. The calcina-
tion/regeneration of the material was carried out in air at 875 C,
under these conditions the CaCO3 will be decomposed to CaO
and CO2 and the catalytic part of the solid will be oxidized to
NiO. To fulll cyclic operation, a NiO pre-reduction step in
10 vol.% H2 at 650 C was carried out previously to the following
SER stage. The experimental information extracted from this
SER/calcination-oxidation cycles will be critical to assess the
performance of the hybrid material. While the behavior of the
CO2 sorbent has been widely analyzed as function of reaction
(SER and calcination) conditions, [8] there are very scarce data
on the behavior of the reforming catalyst after being exposed cycli-
cally to reducing/oxidizing environments [18,21]. In fact, the
results presented in the literature that include the cyclic testing
of hybrid catalyst-sorbent materials are regenerated either under
reducing conditions as Albrecht et al. that kept the same reaction
atmosphere for the SER and the regeneration stages and increased
the reaction temperature up to 850 C to carry out the calcination
703
of the CaCO3 formed; or under inert atmosphere and at a relatively
low temperature [45,61].
Up to seven cycles were tested with the 18.5NiO material, and
the results in terms of H2 and CO2 content in gas product are
shown in Fig. 7. As it can be seen, as a consequence of the cyclic
operation alternating between reforming/carbonation and regen-
eration/calcination, the length of the pre-breakthrough period
slightly diminishes with increasing the number of reaction cycles.
This indicates that the sorbent part of the material still has not
reached its residual CO2 carrying capacity. At this point it is neces-
sary to clarify however, that due to gas analysis limitations, the
compositions plotted in Fig. 7 are obtained after around 45 min
of reforming reaction, therefore, the decrease in CO2 capture capac-
ity is relatively low (a good indicative of the stability of the
sorbent).
With respect to the composition of the gas phase, the differ-
ences among the reaction cycles are not representative and in
every case H2 is over 90 v.% (d.b.). During this period, the produc-
tivity performance is around 0.08 kgH2/kghybrid solid
hour. Once the
CO2 capture is not efcient, and the gas composition tends to the
typical composition of SMR the differences along cycles increase.
For this step in every case, the gas does not fulll equilibrium
composition, and there is a noticeable deactivation of the catalyst
as long as the number of cycles increases. The slight increase in
NiO crystal size that has been determined for the 18.5NiO trough
XRD revealed a slight sintering of the solid that must be
responsible of the poorer performance of the catalytic part of the
material as long as reaction cycles increases. However, and in a
Fig. 7. Evolution of H2, and CO2 content in the gas product stream with time and
number of reaction cycles. Reaction conditions: 650 C, S/C = 3 and 550 h 1 CH4. The
discontinuous lines represent equilibrium composition.
704 A.L. Garca-Lario et al. / Chemical Engineering Journal 264 (2015) 697705
similar trend as found for the experiments carried at lower S/C, the
presence of CaO in the material allows reaching H2 production
close to equilibrium values in SER period.
4. Conclusions
In this work hybrid materials containing the CO2 sorbent and
reforming catalyst have been synthesised through physical mixing
of CaO, powdered NiO and calcium aluminate cement that acted as
a binder and a source of Ca12Al14O33. The materials showed a CO2
carrying capacity of around 20 wt.% of calcined sorbent after being
submitted to 80 carbonation/calcination cycles (calcining condi-
tions 900 C and 70 v.% CO2). The effect of NiO content, and S/C
ratio on H2 yield was analyzed. As it was shown in the experimen-
tal results, the 14NiO and 18.5NiO materials were able to reach
equilibrium compositions for a range of S/C between 1.5 and 3 at
a CH4 spatial velocity of 1200 h 1. Finally, the 18.5NiO material
has been successfully tested cyclically alternating from SER condi-
tions to regeneration (oxidation conditions), and it was able to
reach H2 close to equilibrium compositions (over 90 v.% H2 d.b.)
showing a low deactivation with increasing the reaction cycles.
Acknowledgments
This work acknowledges the support by the R+D Spanish
National Program from the Spanish Ministry of Economy and Com-
petitiveness under project ENE2012-37936-C02-01, the European
Regional Development Fund (FEDER program) and the Regional
Aragon Government (DGA) under the research groups support pro-
gram. The research leading to these results has also received fund-
ing from the European Union Seventh Framework Programme FP7
under Grant agreement n 608512 ASCENT Project. A.L. Garca-
Lario acknowledges the FPI fellowship (project ENE 2009-11353,
BES-2010-032636 nanced by Spanish Ministry of Science and
Innovation MICINN).
References
[1] T. Rostrup-Nielsen, Manufacture of hydrogen, Catal. Today 106 (2005) 293
296.
[2] J.C. Meerman, E.S. Hamborg, T. van Keulen, A. Ramrez, W.C. Turkenburg, A.P.C.
Faaij, Techno-economic assessment of CO2 capture at steam methane
reforming facilities using commercially available technology, Int. J.
Greenhouse Gas Control 9 (2012) 160171.
[3] J.R. Rostrup-Nielsen, J. Sehested, J.K. Norskov, Hydrogen and synthesis gas by
steam and CO2 reforming, Adv. Catal. 47 (2002) 65139.
[4] B. Metz, O. Davidson, H. de Coninck, M. Loos, L. Meyer, IPCC Special Report on
Carbon Dioxide Capture and Storage. Prepared by Working Group III of the
Intergovernmental Panel on Climate Change, in, Cambridge University Press,
Cambridge, United Kingdom and New York, NY, USA, 2005, pp. 442.
[5] IEA, Hydrogen production and storage- R&D Priorities and Gaps, in, 2006.
[6] S. Agrawala, I.A. Bashmakov, G. Blanco, B. J., T. Bruckner, IPCC Special Report on
Climate Change Mitigation, IPCC Special Report on Climate Change Mitigation.
Sumary for policymakers, (2014).
[7] Y.S. Cheng, M.A. Pena, K.L. Yeung, Hydrogen production from partial oxidation
of methane in a membrane reactor, J. Taiwan Inst. Chem. Eng. 40 (2009) 281
288.
[8] D.P. Harrison, Sorption-enhanced hydrogen production: a review, Ind. Eng.
Chem. Res. 47 (2008) 64866501.
[9] B. Balasubramanian, A. Lopez-Ortiz, S. Kaytakoglu, D.P. Harrison, Hydrogen
from methane in a single-step process, Chem. Eng. Sci. 54 (1999) 35433552.
[10] C. Han, D.P. Harrison, Simultaneous shift reaction and carbon dioxide
separation for the direct production of hydrogen, Chem. Eng. Sci. 49 (1994)
58755883.
[11] J.R. Hufton, S. Mayorga, S. Sircar, Sorption-enhanced reaction process for
hydrogen production, AIChE J. 45 (1999) 248256.
[12] A. Lopez Ortiz, D.P. Harrison, Hydrogen Production Using Sorption-Enhanced
Reaction, Ind. Eng. Chem. Res. 40 (2001) 51025109.
[13] K. Johnsen, J.R. Grace, S.S.E.H. Elnashaie, L. Kolbeinsen, D. Eriksen, Modeling of
sorption-enhanced steam reforming in a dual uidized bubbling bed reactor,
Ind. Eng. Chem. Res. 45 (2006) 41334144.
[14] E. Ochoa-Fernandez, G. Haugen, T. Zhao, M. Ronning, I. Aartun, B. Borresen,
Process design simulation of H2 production by sorption enhanced steam
methane reforming: evaluation of potential CO2 acceptors, Green Chem. 9
(2007) 654662.
[15] M.C. Romano, E.N. Cassotti, P. Chiesa, J. Meyer, J. Mastin, Application of the
sorption enhanced-steam reforming process in combined cycle-based power
plants, Energy Procedia 4 (2011) 11251132.
[16] I. Martnez, M.C. Romano, P. Chiesa, G. Grasa, R. Murillo, Hydrogen production
through sorption enhanced steam reforming of natural gas: thermodynamic
plant assessment, Int. J. Hydrogen Energ. 38 (2013) 1518015199.
[17] A.L. Garca-Lario, M. Aznar, I. Martinez, G.S. Grasa, R. Murillo, Experimental
study of the application of a NiO/NiAl2O4 catalyst and a CaO-based synthetic
sorbent on the Sorption Enhanced Reforming process, Int. J. Hydrogen Energ.
(2014), http://dx.doi.org/10.1016/j.ijhydene.2014.10.033.
[18] A.I. Lysikov, A.G. Okunev, O.V. Netskina, Study of a nickel catalyst under
conditions of the SER process: inuence of redox cycling, Int. J. Hydrogen
Energ. 38 (2013) 1035410363.
[19] J. Sehested, J.A.P. Gelten, S. Helveg, Sintering of nickel catalysts: effects of time,
atmosphere, temperature, nickel-carrier interactions, and dopants, Appl. Catal.
A 309 (2006) 237246.
[20] H.S. Roh, K.W. Jun, S.E. Park, Methane-reforming reactions over Ni/Ce-ZrO2/h-
Al 2O3 catalysts, Appl. Catal. A 251 (2003) 275283.
[21] A.L. Garca-Lario, M. Aznar, G.S. Grasa, T. Garca, R. Murillo, Study of nickel
catalysts for hydrogen production in sorption enhanced reforming process, J.
Power Sources 242 (2013) 371379.
[22] T. Numaguchi, K. Kikuchi, Ind. Eng. Chem. Res. 30 (1991) 447453.
[23] P.H. Bolt, S.F. Lobner, T.P. Van den Bout, J.W. Geus, F.H.P.M. Habraken, Appl.
Surf. Sci. 7071 (1993) 196199.
[24] Z. Jian, A. Tong, Z. Xiongfu, W. Liu, H. Liu, J. Qiu, K.L. Yeung, New synthesis
strategies for Ni/Al2O3-Sil-1 core shell catalysts for steam reforming of
methane, Catal. Today 236 (2014) 3440.
[25] B.Y. Kwang, D.P. Harrison, Low-pressure sorption-enhanced hydrogen
production, Ind. Eng. Chem. Res. 44 (2005) 16651669.
[26] Z.Z.M. Xie, Y. Qi, Z. Cheng, W. Yuan, Sorption-enhanced steam methane
reforming by in situ CO2 capture on a CaOCa9Al6O18 sorbent, Chem. Eng. J.
207208 (2012) 150.
[27] E.A.Y. Ding, Adsorption-enhanced steam-methane reforming, Chem. Eng. Sci.
55 (2000) 3940.
[28] B. Arstad, J. Prostak, R. Blom, Continuous hydrogen production by sorption
enhanced steam methane reforming (SE-SMR) in a circulating uidized bed
reactor: sorbent to catalyst ratio dependencies, Chem. Eng. J. 189190 (2012)
413421.
[29] K. Johnsen, H.J. Ryu, J.R. Grace, C.J. Lim, Sorption-enhanced steam reforming of
methane in a uidized bed reactor with dolomite asCO2-acceptor, Chem. Eng.
Sci. 61 (2006) 11951202.
[30] A. Silaban, D.P. Harrison, High-temperature capture of carbon dioxide:
characteristics of the reversible reaction between CaO(s) and CO2(g), Chem.
Eng. Commun. 137 (1995) 177190.
[31] J.C. Abanades, The maximum capture efciency of CO2 using a carbonation/
calcination cycle of CaO/CaCO3, Chem. Eng. J. 90 (2002) 303306.
[32] J. Blamey, E.J. Anthony, J. Wang, P.S. Fennell, The calcium looping cycle for
large-scale CO2 capture, Prog. Energy Combust. Sci. 36 (2010) 260279.
[33] W. Liu, H. An, C. Qin, J. Yin, G. Wang, B. Feng, M. Xu, Performance enhancement
of calcium oxide sorbents for cyclic CO2 capture-a review, Energy Fuels 26
(2012) 27512767.
[34] Z.S. Li, N.S. Cai, Y.Y. Huang, H.J. Han, Synthesis, experimental studies, and
analysis of a new calcium-based carbon dioxide absorbent, Energy Fuels 19
(2005) 14471452.
[35] Z.S. Li, N.S. Cai, Y.Y. Huang, Effect of preparation temperature on cyclic CO2
capture and multiple carbonationcalcination cycles for a new Ca-based CO2
sorbent, Ind. Eng. Chem. Res. 45 (2006) 19111917.
[36] R. Pacciani, C.R. Mller, J.F. Davidson, J.S. Dennis, A.N. Hayhurst, Synthetic Ca-
based solid sorbents suitable for capturing CO2 in a uidized bed, Can. J. Chem.
Eng. 86 (2008) 356366.
[37] C.S. Martavaltzi, A.A. Lemonidou, Parametric study of the CaOCa12Al14O33
synthesis with respect to high CO2 sorption capacity and stability on multi
cycle operation, Ind. Eng. Chem. Res. 47 (2008) 95379543.
[38] V. Manovic, E.J. Anthony, CaO-based pellets supported by calcium aluminate
cements for high-temperature CO2 capture, Environ. Sci. Technol. 43 (2009)
71177122.
[39] J. Mastin, A. Aranda, J. Meyer, New synthesis method for CaO-based synthetic
sorbents with enhanced properties for high-temperature CO2-capture, Energy
Procedia 4 (2011) 11841191.
[40] Z.S. Li, Y. Liu, N.S. Cai, Understanding the effect of inert support on the
reactivity stabilization for synthetic calcium based sorbents, Chem. Eng. Sci. 89
(2013) 235243.
[41] V. Manovic, E.J. Anthony, The long-term behavior of CaO-based pellets
supported by calcium aluminate cements in long series of CO2 capture
cycles, Ind. Eng. Chem. Res. 48 (2009) 89068912.
[42] J.A. Satrio, B.H. Shanks, T.D. Wheelock, Development of a novel combined
catalyst and sorbent for hydrocarbon reforming, Ind. Eng. Chem. Res. 44 (2005)
39013911.
[43] C.S. Martavaltzi, A.A. Lemonidou, Hydrogen production via sorption enhanced
reforming of methane: development of a novel hybrid materialreforming
catalyst and CO2 sorbent, Chem. Eng. Sci. 65 (2010) 41344140.
[44] N. Chanburanasiri, A.M. Ribeiro, A.E. Rodrigues, A. Arpornwichanop, N.
Laosiripojana, P. Praserthdam, S. Assabumrungrat, Hydrogen production via
 A.L. Garca-Lario et al. / Chemical Engineering Journal 264 (2015) 697705
sorption enhanced steam methane reforming process using Ni/CaO
multifunctional catalyst, Ind. Eng. Chem. Res. 50 (2011) 1366213671.
[45] J.N. Kim, C.H. Ko, K.B. Yi, Sorption enhanced hydrogen production using one-
body CaOCa12Al14O33Ni composite as catalytic absorbent, Int. J. Hydrogen
Energ. 38 (2013) 60726078.
[46] J.A. Satrio, B.H. Shanks, T.D. Wheelock, A combined catalyst and sorbent for
enhancing hydrogen production from coal or biomass, Energy Fuels 21 (2007)
322326.
[47] K.O. Albrecht, J.A. Satrio, B.H. Shanks, T.D. Wheelock, Application of a
combined catalyst and sorbent for steam reforming of methane, Ind. Eng.
Chem. Res. 49 (2010) 40914098.
[48] V. Manovic, E.J. Anthony, CaO-based pellets with oxygen carriers and catalyst,
Energy Fuels 25 (2011) 48464853.
[49] V. Manovic, E.J. Anthony, Integration of calcium and chemical looping
combustion using composite CaO/CuO-based materials, Environ. Sci.
Technol. 45 (2011) 1075010756.
[50] V.R. Choudhary, A.M. Rajput, A.S. Mamman, NiO alkaline earth oxide catalysts
for oxidative methane to syngas conversion: inuence of alkaline earth oxide
on the surface properties and temperature programmed reduction reaction by
H2 and methane, J. Catal. 178 (1998) 576585.
[51] Z.L. Zhang, X.E. Verykios, Carbon dioxide reforming of methane to synthesis
gas over supported Ni catalyst, Catal. Today 21 (1994) 589595.
[52] K.O. Christensen, D. Chen, R. Lodeng, A. Holmen, Effect of supports and Ni
crystal size on carbon formation and sintering during steam methane
reforming, Appl. Catal. A 314 (2006) 922.
705
[53] M.E. Agnelli, M.C. Demicheli, E.N. Ponzi, Catalytic deactivation of methane
steam reforming catalysts. 1. Activation, Ind. Eng. Chem. Res. 26 (1987) 1704
1707.
[54] W.S. Dong, H.S. Roh, K.W. Jun, S.E. Park, Y.S. Oh, Methane reforming over
Ni/Ce-ZarO2 catalysts: effect of nickel content, Appl. Catal. A 226 (2002)
6372.
[55] M.A. Goula, A.A. Lemonidou, A.M. Estathiou, Characterization of carbonaceous
species formed during reforming of CH4 with CO2 over Ni/CaOAl2O3
catalysts studied by various transient techniques, J. Catal. 161 (1996)
626640.
[56] G.S. Grasa, J.C. Abanades, CO2 capture capacity of CaO in long series of
carbonation/calcination cycles, Ind. Eng. Chem. Res. 45 (2006) 88468851.
[57] I. Lysikov, N. Salanov, G. Okunev, Change of CO2 carrying capacity of CaO in
isothermal recarbonationdecomposition cycles, Ind. Eng. Chem. Res. 46
(2007) 46334638.
[58] P. Sun, C.J. Lim, J.R. Grace, Cyclic CO2 capture by limestone-derived sorbent
during prolonged calcination/carbonation cycling, AIChE J. 54 (2008) 1668
1677.
[59] J.S. Dennis, R. Pacciani, The rate and extent of uptake of CO2 by asynthetic,
CaO-containing sorbent, Chem. Eng. Sci. 64 (2009) 21472157.
[60] V. Manovic, E.J. Anthony, Carbonation of CaO-based sorbents enhanced by
steam addition, Ind. Eng. Chem. Res. 49 (2010) 91059110.
[61] H.R. Radfarnia, M.C. Iliuta, Development of Al-stabilized CaO-nickel hybrid
sorbent-catalyst for sorption-enhanced steam methane reforming, Chem. Eng.
Sci. 109 (2014) 212219.