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Hydrogen production by a Fe-based oxygen carrier


and methane-steam redox process:
Thermodynamic analysis

pez-Ortiz, M.J. Melendez-Zaragoza, V. Collins-Martı́nez*


A. Lo
Centro de Investigaci
on en Materiales Avanzados, S.C., Miguel de Cervantes 120, Complejo Industrial Chihuahua,
Chihuahua, Chihuahua, Mexico

article info abstract

Article history: The performance of iron oxide FeO/Fe3O4 redox pair as an oxygen carrier was investigated
Received 7 June 2017 for hydrogen (H2) and/or syngas (H2þCO) production through a methane-steam chemical
Accepted 17 July 2017 looping process using thermodynamic analysis and process simulation by Aspen Plus to
Available online xxx find optimal reactions conditions (ORC). The reaction system was divided in two reactors.
In the fuel reactor (FR) the following reactions were targeted: ¼ CH4(g) þ Fe3O4 ¼ 3FeO þ ¼
Keywords: CO2(g) þ ½ H2O(g) and CH4(g) þ Fe3O4 ¼ 3FeO þ 2H2(g) þ CO(g) where the CH4/Fe3O4 molar
Methane-steam redox process ratio was varied from 0.25 to 1 and 300e900  C. In the steam oxidation reactor (SR), the solid
Oxygen carrier products from FR were combined with steam to produce: 3FeO þ H2O(g) ¼ Fe3O4 þ H2(g) in a
Thermodynamic analysis T range of 300e900  C. Results indicate that ORC in the reduction reactor consists in T ¼ 650
e700  C and CH4/Fe3O4 ¼ 0.75e1, While for the SR were T ¼ 520e600  C.
© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

scale, since small-scale plants make hydrogen production


Introduction uneconomical. Therefore, large centralized industrial plants
have been found to be the most cost-effective [1]. World
Hydrogen, apart from being an important industrial chemical consumption of hydrogen is projected to increase 3.5%
worldwide, can be considered as the choice of carrier for the annually through 2018 to more than 300 billion cubic meters
emerging renewable energy generation technologies. How- and is expected to grow to about 5e6% in the next five years
ever, today hydrogen production relies on the use of fossil [2]. Hence, an alternate approach that may include the use of
fuels, being steam methane reforming (SMR) the preferred near and remote natural gas reserves, especially those coming
route for the industrial production of hydrogen, since it ac- from the recent shale gas sites being explored worldwide, is
counts for more than a half of the world hydrogen production. needed for more cost-effective small scale H2 production.
SMR is a highly endothermic catalytic reaction Consequently, there is a renewed interest in the old and
(DH 298K ¼ 206 kJ/mol), which takes place in a temperature mature steam-iron process [3]. This process, in principle, is
range of 700e850  C according to: one of the few processes that do not require the step of gas
Reaction 1 : CH4ðgÞ þ H2 OðgÞ ¼ 3H2ðgÞ þ COðgÞ separation to produce a high purity hydrogen stream at small
scale. This process involves a series of the redox reactions,
The economic feasibility of SMR units are restricted by where the reduction of iron oxide with syngas (a mixture of CO

* Corresponding author.
E-mail address: virginia.collins@cimav.edu.mx (V. Collins-Martı́nez).
http://dx.doi.org/10.1016/j.ijhydene.2017.07.130
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

 pez-Ortiz A, et al., Hydrogen production by a Fe-based oxygen carrier and methane-steam redox
Please cite this article in press as: Lo
process: Thermodynamic analysis, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.07.130
2 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 x x x ( 2 0 1 7 ) 1 e1 3

and H2) is followed by the oxidation of the reduced metallic structural stabilization of ceria-zirconia solid solutions sup-
iron with steam according to the following reactions: ported on alumina towards the CO oxidation catalysis. The
unique oxygen storage capacity of the CeO2eZrO2 combined
Reaction 2 : Fe3 O4 þ 4COðgÞ ¼ 3Fe þ 4CO2ðgÞ
with iron oxides produced an oxygen carrier that combines
this important feature with the thermal stability and activity
Reaction 3 : Fe3 O4 þ 4H2ðgÞ ¼ 3Fe þ 4H2 OðgÞ as confirmed by several research studies [12e14].
Moreover, several researchers [15e19] have proposed a
Reaction 4 : 3Fe þ 4H2 OðgÞ ¼ Fe3 O4 þ 4H2ðgÞ novel two-step SMR process for hydrogen production based on
This process make use of a metal oxide (Fe3O4) as an oxy- the chemical looping concept and a scheme of this is pre-
gen carrier to perform the redox reactions (2e4) and at the sented in Fig. 1.
same time serves as a heat transfer medium between the two In the fuel reactor (I) the oxygen carrier, typically a metal
reactors (reduction and oxidation) in a cycle reaction loop in oxide (MeO), is reacted with methane to produce syngas and
order to make a continuous process and to increase energy the reduced metal (Me) according to:
efficiency. Gaseous carbon oxides rich stream is achieved after Reaction 6 : CH4ðgÞ þ MeO ¼ Me þ 2H2ðgÞ þ COðgÞ
steam condensation from the reduction reactor (reactions 2
and 3) and a high purity hydrogen stream can be obtained
Reaction 7 : H2 OðgÞ þ Me ¼ MeO þ H2ðgÞ
after steam condensation from the oxidation reactor (reaction
4). Due to the significant characteristics of this process, this Finally, the regenerated oxygen carrier is sent back to the
has been used as a reference for the production of H2 in the fuel reactor to complete one full loop or reaction cycle. The
chemical looping combustion [4] and H2 storage [5]. combination of reactions (6) and (7) leads to reaction (1), which
For the specific case of the reduction of iron oxide with a is the SMR reaction. The reaction process indicated in Fig. 1 is
gas fuel such as methane and the redox iron pair being Fe3O4/ usually called as chemical looping steam methane reforming
FeO the following reaction applies: (CL-SMR). This process separate the feed of methane and
steam in two step reactors thus, producing a syngas stream in
1 1 1
Reaction 5 : Fe3 O4 þ CH4ðgÞ ¼ 3FeO þ CO2ðgÞ þ H2 O the first and a H2 gas product in the second that needs no
4 4 4
further purification.
Even though several other metal oxides have been pro- One critical issue of this proposed reaction scheme deals
posed under the chemical looping concept for hydrogen pro- with the relatively low reactivity of the oxygen carrier towards
duction, the Fe3O4/Fe redox system is one of the most studied the reoxidation of the reduced metal (reaction 7). Several
systems due to the fact that employs inexpensive materials metal oxides have been reported as oxygen carriers for the CL-
and because it produces a high yield of H2 per mass of iron SMR such as Fe3O4, WO3, SnO2, NieFe, (Zn, Mn)eFe, CueFe and
(48 g H2/kg Fe, from equation 4). One of the main challenges of Ce-based oxides [15]. Among all these oxygen carriers such as
a looping operation of the steam-iron process lies in the Fe-oxides have proven to be suitable for the CL-SMR.
temperature swings and different gaseous atmospheres that
the material needs to be exposed in order to perform a cycle
operation in the process. This operation mode, performed at
high temperatures, often produce sintering in the material
with the consequent loss of activity and this being reflected in
a significant decrease of lifetime, thus reducing the overall
efficiency of the process.
In order to overcome this issue, several studies have
concentrated in improving reactor kinetics and the stability of
the materials by modifying iron oxide with the addition of
metals like Al, Mo and Ce as reported by Otsuka et al. [6].
Takenaka et al. [7] employed a mixture of NieCreFeOx, which
reacted with methane followed by reaction with steam to
produce pure hydrogen, where Cr species in NieCreFeOx
were stabilized as octahedral Crþ 3 O6 in the ferrites CrxFe3xO4
during the redox reactions. It was concluded that Cr helped to
inhibit sintering of iron species. While Urasaki et al. [8] added
palladium and zirconia to the iron-based oxygen carrier to
accelerate both the reduction and oxidation rates and also
found that zirconia enhanced structural and thermal stability
in iron oxides. Zafar et al. [9] used SiO2 and MgAl2O4 as sup-
ports to reduce the sintering of iron oxide, while Galvita and
Sundmacher [10] proposed the use of Cr2O3eFe3O4eCeO2e
ZrO2 to provide stability to the oxygen carrier up to 100 redox
cycles. However, some carbon monoxide in the hydrogen
product stream was observed during the re-oxidation phase,
whereas Liotta et al. [11] examined the redox behavior and Fig. 1 e Conceptual scheme of the SMR chemical looping.

 pez-Ortiz A, et al., Hydrogen production by a Fe-based oxygen carrier and methane-steam redox
Please cite this article in press as: Lo
process: Thermodynamic analysis, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.07.130
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 x x x ( 2 0 1 7 ) 1 e1 3 3

Nevertheless, thermodynamic constrains for the hydrogen to produce a high purity CO2 stream ready for sequestration,
evolution make this oxygen carrier to behave in a complex while the oxidation of FeO to Fe3O4 with steam produced a
way, since in some cases the complete reduced Fe phase is high purity hydrogen stream. They found that reduction to Fe,
required for a high H2 production yield, while the complete rather than FeO, in step 1 gave low levels of H2 and after 10
oxidation with steam beyond Fe3O4 is thermodynamically cycles of reduction and oxidation led to the deposition of
limited [17]. However, this oxygen carrier can be considered carbon at lower temperatures. Furthermore, Svoboda et al.
ideal for CL-SMR applications and this is based on its reduced [29] studied the thermodynamic and chemical equilibrium of
propensity to carbon formation and resistance to form ag- the reduction of Fe3O4 by CH4 and oxidation of iron by steam.
glomerates. These last features are critical for an oxygen The study was concentrated on finding convenient conditions
carrier to retain its activity over continuous redox cycles. for reduction of Fe3O4 to iron at temperatures from 400 to
Furthermore, iron oxide oxygen carriers are not susceptible to 800 K, but also on the possible formation of undesired soot,
form sulfide or sulfate compounds under sulfur-containing Fe3C and iron carbonate. Reduction of magnetite with
atmospheres [20], while large natural reserves and low cost methane did not produce iron carbides or carbonates,
make them suitable for implementation at large scales whereas conditions favored the formation of Fe and CO2, and
[21e23]. Some drawbacks of these Fe-based oxygen carriers H2O as gas products.
include weak redox characteristics, relatively low oxygen From all previous thermodynamic studies related to the
storage capacity (OSC), and limited reactivity towards gaseous use of iron oxides as oxygen carrier for the complete oxidation
fuels like methane [24]. of methane (reactions 2 and 3) or the partial oxidation of
Additionally, Fe presents multiple oxidation states such as methane, which is a special case of the so-called chemical
Fe2O3, Fe3O4, FeO and Fe and as indicated above it presents looping steam methane reforming (CL-SMR) that involve the
thermodynamic limitations, since only the transformation partial oxidation of methane through:
from Fe2O3 to Fe3O4 is feasible for the total oxidation of
Reaction 8 : 3Fe2 O3 þ CH4ðgÞ ¼ 2Fe3 O4 þ 2H2ðgÞ þ COðgÞ
methane, whereas partial oxidation of methane (POX) is
favored in the transition reduction from FeO to Fe according to
Monzam et al. [25]. Reaction 9 : Fe3 O4 þ CH4ðgÞ ¼ 3FeO þ 2H2ðgÞ þ COðgÞ

Thermodynamic considerations Reaction 10 : FeO þ CH4ðgÞ ¼ Fe þ 2H2ðgÞ þ COðgÞ

Several thermodynamic analyses have studied different ap- Reaction 11 : 3FeO þ H2 OðgÞ ¼ Fe3 O4 þ H2ðgÞ
proaches to the CL-SMR process. Fraser et al. [25] performed a
These last reactions present the advantage to produce a
thermodynamic analysis of the reformer sponge iron cycle
syngas mixture in the iron reduction reactor (reactions 8e10),
(RESC) process that consisted in the hydrogen production
while the regeneration of the reduced Fe with steam is able to
including a hydrocarbon reformer and a sponge iron reactor
produce a high purity H2 stream. However, this regeneration
(SIR). The reformer output gas (H2 and CO) reduced the pellets
will only produce Fe3O4 as reaction (11) is thermodynamically
from magnetite (Fe3O4) and wuestite (FeO) into iron metal (Fe)
limited. Therefore, in a cyclic operation the redox reaction
through reactions (2) and (3) and the reduced Fe is reoxidized
between the two reactors of Fig. 1 will only be reactions (9) and
with steam by reaction (4). They found that the process offers
(11). However, carbon deposition during the operation is
hydrocarbon to hydrogen conversion efficiencies in the order
another important aspect to be considered in this process
of 75% vs LHV for methane and at a temperature range of
through the Boudouard and methane pyrolysis reactions:
750  C and above. Steinfeld and Kuhn [26] presented a high
temperature thermochemistry analysis of the Fe3O4 reduction Reaction 12 : 2COðgÞ ¼ CO2ðgÞ þ C
with methane for the production of syngas. They studied the
reaction system at temperatures above 1000  C aimed for the Reaction 13 : CH4ðgÞ ¼ 2H2ðgÞ þ C
use of concentrated solar radiation as the energy source. They
found that a mixture of 66.7% H2 and 33.3% CO can be ach- Galvita and Sundmacher [30] studied the CL-SMR reaction
ieved with complete reduction to metallic Fe. Kang et al. [27] system and concluded that at a reduction of approximately
performed a thermodynamic analysis of the three-reactor 60% of the Fe2O3 carbon formation was avoided. Further
chemical-looping process (TRCL), which consisted in a fuel reduction towards Fe produced carbon deposits on the oxygen
reactor, a steam reactor, and an air reactor. In the fuel reactor, carrier. Therefore, the restrictions in order to avoid carbon
natural gas (mainly CH4) is oxidized to CO2 and H2O by the formation and the steam oxidation of the reduced iron lead to
lattice oxygen of the oxygen carrier (Fe2O3, WO3, and CeO2). In select the Fe3O4/FeO as the ideal redox pair for the CL-SMR
the steam reactor, the steam is reduced to hydrogen through process.
oxidation of the reduced oxygen carrier, while in the air Up to date, no thermodynamic analysis have been per-
reactor; the oxygen carrier is fully oxidized by air. Results formed to explore optimal reactions conditions. From one
indicated a hydrogen production of 2.64 mol H2 per mol CH4 end: complete oxidation of methane by Fe3O4 (steam iron
under thermo-neutral conditions and this was affected process, SIP, which produce only CO2 and FeO in the reduction
mainly by the steam-conversion rate. Bohn et al. [28] studied reactor) to the other end: partial oxidation of methane (POX-
the hydrogen production with simultaneous capture of CO2 MeO or CL-SMR, where syngas and FeO is produced) and
using the redox reactions of iron oxides in packed beds. They subsequent hydrogen production from reoxidation of FeO.
examined the thermodynamics of exposing Fe2O3 to a syngas Furthermore, most of the previously reported thermodynamic

 pez-Ortiz A, et al., Hydrogen production by a Fe-based oxygen carrier and methane-steam redox
Please cite this article in press as: Lo
process: Thermodynamic analysis, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.07.130
4 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 x x x ( 2 0 1 7 ) 1 e1 3

analyses have not considered the very important carbon for- reaction (11). In this reactor the FeO/H2O feed molar ratio was
mation in their calculations, which avoidance will certainly varied from 3 (stoichiometric value according to reaction (11))
mislead the entire reaction system predicted equilibrium to 0.546. This represents a gradual increase from 1 kmol/h of
compositions and reactions yields. This proposed process H2O per 3 kmol/h of FeO up 6 kmol/h of H2O per 3 kmol/h of
operation aims to restrict the oxidation states between the FeO. This feed steam variation was aimed to find the minimum
two reactors of Fig. 1 to the Fe3O4/FeO redox pair, while amount of steam needed in order to regenerate FeO to Fe3O4 at
avoiding carbon formation to insure a high purity hydrogen a reasonable oxidation temperature, where kinetics are
stream from the steam oxidation reactor. favorable (500e600  C) [33]. It is important to notice that all the
Therefore, the aim of the present investigation is to present simulation calculations are based on theoretical
perform a thermodynamic and process simulation studies to thermodynamic considerations and these are to be taken as a
find optimal operating conditions (avoiding carbon formation) guide to further experimental evaluation of the reaction sys-
close to equilibrium for a high H2 and/or syngas production. In tems, since no heat and mass diffusional limitations as well as
addition, these under the SIP/CL-SMR reaction system using kinetics effects were taken into account for the conformation
methane as a feed (for the fuel reactor) and steam (for the of the present thermodynamic analysis.
oxidation reactor), while employing the Fe3O4/FeO redox pair
between the reduction and oxidation reactors. This analysis Process simulation method
will include the evaluation of the thermodynamic equilibrium
composition of the reaction system, the behavior of the Fe3O4/ Process simulation calculations was performed using the
CH4 and H2O/FeO feed molar ratios as a function of tempera- Aspen-Plus© Engineering Process Simulator. This is a program
ture and product compositions for the reduction and oxida- for simulation of chemical processes in which the analysis of
tion reactors, respectively. Furthermore, it is expected that the chemical processes as well as heat integration can be made.
feed molar ratio of Fe3O4 to CH4 will determine the operation This simulator was employed for the analysis of the process
mode of the process from complete oxidation (SIP) to a partial scheme of Fig. 2. The module of Aspen-Plus that was used to
oxidation of methane (CL-SMR). Consequently, a process evaluate the reaction systems were: the RGibbs (Gibbs
simulation will examine oxygen carrier recirculation from the Reactor), wherein RGibbs method is based on the Gibbs free
oxidation to the reduction reactors and its influence on the energy minimization technique for multiphase reactions and
process operating conditions. material balance, cyclone units were used to separate solid
and gas streams.

Methods
Results and discussion
Thermodynamics method
Thermodynamic analysis
Thermodynamic calculations in the present study were per-
formed by the Gibbs free energy minimization technique The fuel reactor
GFEM. In a reaction system where many simultaneous re- This section presents results from the equilibrium amounts of
actions take place, equilibrium calculations can be performed H2, CO, CO2, CH4 and C, Fe, FeO, Fe2O3 and Fe3O4 from the fuel
through GFEM approach (also called the nonstoichiometric reactor in a temperature range of 300e900  C and CH4/Fe3O4
method). Details of this technique can be found elsewhere feed molar ratios from 0.25 to 1. At the studied conditions the
[31,32]. All calculations were performed using the ASPEN Plus® conversion of methane was gradually increased from about
RGIBBS reactor model and the RedlicheKwong equation of 4% at 300  C, 90% at 500  C and up to 99.9% at 600  C. This is
state for correction of non-ideal conditions. In a RGIBBS associated to the intrinsic equilibrium reactivity of a solid
reactor the equilibrium composition of all possible combina- Fe3O4 with respect to a gaseous fuel such as CH4 and avail-
tion of reactions that are able to take place within the ther- ability of the metal oxide lattice oxygen into the gas phase.
modynamic system are considered. The RGIBBS program of Fig. 3 shows the equilibrium production of H2 (3a) and CO (3b)
this reactor finds the most stable phase combination and es- from the fuel reactor (dry basis) in kmol/h as a function of
tablishes the phase compositions where the Gibbs free energy temperature and CH4/Fe3O4 feed molar ratio.
of the reaction system reaches its minimum at a fixed mass At low temperatures (300e500  C) and where CH4/Fe3O4
balance, constant pressure, and temperature. For the oxida- ratio is small (below 0.5), there is no enough temperature and/
tion of methane and regeneration of the iron oxide species the or oxygen available for the reaction between Fe3O4 and
gaseous species included were: CH4, CO, CO2, H2, and H2O, methane to produce syngas (CO þ H2) and therefore, this
while solid species were: C, Fe, FeO, Fe2O3, F3C, and FeCO3. metal oxide is poorly reactive towards reaction (9). However,
For the fuel reactor the temperature was varied in the range the small reactivity in this region is attributed to the complete
of 300e900  C at 1 atm. While, the CH4/Fe3O4 feed molar ratio oxidation of methane by Fe3O4 (reaction 5) where at the SIP
was varied from 0.25 (stoichiometric value according to reac- conditions (CH4/Fe3O4 ¼ 0.25 and higher but not greater than
tion (5)) to 1 (stoichiometric value according to reaction (9)). 0.5) the production of CO2 and H2O dominate. Greater tem-
Whereas, for the oxidation reactor the temperature was also peratures than 500  C and CH4/Fe3O4 ratios than 0.5 will lead to
varied in the range of 300e900  C at 1 atm. The solid product of the promotion of the partial oxidation of methane by Fe3O4 to
the fuel reactor was fed to the steam oxidation reactor. In this form syngas through reaction (9) according to results pre-
reactor, the FeO is to be reacted with steam according to sented in Fig. 3(a) and (b).

 pez-Ortiz A, et al., Hydrogen production by a Fe-based oxygen carrier and methane-steam redox
Please cite this article in press as: Lo
process: Thermodynamic analysis, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.07.130
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 x x x ( 2 0 1 7 ) 1 e1 3 5

Fig. 2 e Process simulation flowsheet.

Fig. 4(a) and (b) present results of formed CO2 and byproduct. Fig. 5(b) show that the carbon free operating win-
unreacted CH4 contents in the gas product from the fuel dows of the fuel reactor are as follows: from CH4/
reactor, respectively. Fe3O4 ¼ 0.25e0.375 no carbon is present in a temperature
In Fig. 4(a) it is evident that at low temperatures (T < 500  C) range of 480e900  C, CH4/Fe3O4 ¼ 0.5 from 580 to 900  C, CH4/
and small CH4/Fe3O4 ratios, CO2 formation is favored, which is Fe3O4 ¼ 0.625 from 660 to 900  C and CH4/Fe3O4 ¼ 0.75e1 from
the region where complete oxidation of methane is promoted 700 to 900  C. These free carbon regions that can be seen in
and the CO2 content is reduced as the available oxygen con- Fig. 5(b) is where either the Boudouard and/or the methane
tent is increased as the CH4/Fe3O4 ratio is also grown. Also in decomposition reactions (12 and 13) are not thermodynami-
Fig. 4(b) it is evident that methane reactivity is high at low cally favorable. These results agree well with experimental
oxygen lattice content (Fe3O4) and this is reflected in small results reported by Tang et al. [34].
methane content in the product gas at temperatures greater A more careful analysis of the generated data allows to
than around 500  C and small CH4/Fe3O4 ratios (smaller than conclude that according to the previous thermodynamic
0.5). Here in this plot the gradual increase in methane con- analysis optimum conditions in order to produce a maximum
version is clear that increases as temperature rises and the hydrogen production and carbon free operation is at
CH4/Fe3O4 ratio decrease, which is translated in the promotion T ¼ 650e700  C and CH4/Fe3O4 ¼ 0.75e1. It is important to
of the partial oxidation of methane reaction with Fe3O4 (oxy- indicate that no metallic iron (Fe) was present at the studied
gen starving conditions, reaction 9). fuel reactor conditions.
Moreover, Fig. 5(a) and (b) describe the behavior of the FeO
and C solid content at the effluent stream from the fuel reactor The oxidation reactor
of Fig. 1. This section presents results from the equilibrium amounts of
In Fig. 5(a) the maximum conversion from Fe3O4 to FeO at a H2 and Fe3O4 from the oxidation reactor in a temperature
feed of 1 kmol/h of Fe3O4 is according to reaction (5) of 3 kmol/ range of 500e600  C and H2O feed molar flowrate range from 1
h and that means that the iron(II) oxide is the chemical species to 6 kmol/h. At the studied conditions, it is expected to find the
that in the next reactor can be combined with the appropriate minimum amount of steam per three kmols of FeO at a
amount of steam to produce a pure hydrogen stream. There- reasonable temperature from 500 to 600  C, where the reaction
fore, optimal reaction conditions will be those where com- kinetics are reported to be favorable [33]. Fig. 6(a) and (b)
plete conversion of Fe3O4 to FeO is achieved and those are presents results from the oxidation reactor at conditions
where the amount of FeO in Fig. 5(a) is 3 kmol/h. From this above described.
figure, it is clear that those conditions are achieved at tem- In plot 6 (a) the maximum hydrogen production can be
peratures between 500 and 700  C at all CH4/Fe3O4 ratios. At seen as a function of temperature and the feed molar flow to
those conditions, methane is able to reduce magnetite to the reactor. From this figure, it is evident that there is a
iron(II) oxide either through complete or partial oxidation of defined region where the maximum hydrogen production is
methane. However, not only at those conditions magnetite is achieved, which happens to be of 1 kmol/h. These conditions
also thermodynamically stable, greater temperatures from increase as the amount of steam and temperature both in-
700 up to 900  C in a CH4/Fe3O4 range from 0.375 to 0.625 will crease. For example, at 500  C a minimum range of
also insure the production of magnetite and these last con- 3.4e6 kmol/h of steam is needed in order to produce the
ditions match with partial oxidation of methane through maximum amount of hydrogen according to reaction (11),
equation (9). while at 550  C a range of steam of 4.6e6 kmol/h are needed to
Also important in the present investigation is to find obtain the maximum possible H2 production. Finally, at 600  C
operating conditions where no carbon formation is feasible, 6 kmol/h of steam or greater are needed for this purpose.
since any carbon contamination over the oxygen carrier will However, research points out that H2 evolution via water
be gasified in the oxidation reactor, thus producing carbon splitting reaction (11) requires Fe phase to be as fully reduced
dioxide gases that will ultimately combine with the expected as possible, while it is thermodynamically limited for Fe phase
hydrogen production and consequently become a gaseous to be completely oxidized beyond Fe3O4 using steam [34].

 pez-Ortiz A, et al., Hydrogen production by a Fe-based oxygen carrier and methane-steam redox
Please cite this article in press as: Lo
process: Thermodynamic analysis, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.07.130
6 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 x x x ( 2 0 1 7 ) 1 e1 3

Fig. 3 e Equilibrium content of H2 (a) and CO (b) for the fuel reactor.
 pez-Ortiz A, et al., Hydrogen production by a Fe-based oxygen carrier and methane-steam redox
Please cite this article in press as: Lo
process: Thermodynamic analysis, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.07.130
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 x x x ( 2 0 1 7 ) 1 e1 3 7

Fig. 4 e Equilibrium content of CO2 (a) and CH4 (b) for the fuel reactor.

 pez-Ortiz A, et al., Hydrogen production by a Fe-based oxygen carrier and methane-steam redox
Please cite this article in press as: Lo
process: Thermodynamic analysis, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.07.130
8 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 x x x ( 2 0 1 7 ) 1 e1 3

Fig. 5 e Equilibrium content of FeO (a) and C (b) for the fuel reactor.

 pez-Ortiz A, et al., Hydrogen production by a Fe-based oxygen carrier and methane-steam redox
Please cite this article in press as: Lo
process: Thermodynamic analysis, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.07.130
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 x x x ( 2 0 1 7 ) 1 e1 3 9

Fig. 6 e Equilibrium content of H2 (a) and H2O (b) for the oxidation reactor.

 pez-Ortiz A, et al., Hydrogen production by a Fe-based oxygen carrier and methane-steam redox
Please cite this article in press as: Lo
process: Thermodynamic analysis, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.07.130
10 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 x x x ( 2 0 1 7 ) 1 e1 3

Moreover, other research indicate that the reduction from reactor are presented. Here, CO2 mol fraction in dry-basis (DB)
Fe3O4 to Fe promotes carbon deposition [30]. is 0.77, while H2 is only 0.17 with traces of CO (0.06) with no
Furthermore, Fig. 6(b) presents the Fe3O4 content at presence of unreacted CH4. These results are consistent with
different steam feed to the oxidation reactor. Here in this plot, the promotion of reaction (5) conducing to a complete oxida-
it can be seen that the only conditions where complete con- tion of methane to produce FeO (2.80 kmol/h) as observed in
version of FeO to Fe3O4 is achieved at regions where the Table 1.
amount of steam and temperature both increase. These re- According to Fig. 2, gases and solids are separated in
sults mimic the same conditions where the maximum streams GASP-1 and INPUT-2, where this last is fed to the
hydrogen production is achieved from Fig. 5(a). Therefore, this oxidation reactor together with stream STEAM, which con-
regenerated 1 kmol/h of Fe3O4 is expected to be recirculated sists of 6 kmol/h at a reactor temperature of 600  C. Stream
back to the fuel reactor. OUTPUT-2 contains the products from the oxidation reactor
where 0.93 kmol/h of H2 combined with 1 kmol/h of Fe3O4 and
Process simulation 5 kmols/h of excess steam are produced. This stream is
separated in H2PROD and RECIRC streams, where this last one
Fig. 1 presents a diagram of the process scheme employed is stent back to the fuel reactor. The H2PROD stream contains a
during the simulation of the SIP/CL-SMR reaction system with very high concentration of H2 (mol fraction of 1, dry basis) and
either the production of pure CO2 or a syngas stream from the once this water is separated in this stream, pure H2 can be
fuel reactor, while in the oxidation reactor the H2 evolution obtained. The yield of this process based on the hydrogen
and iron oxide regeneration is achieved. Table 1 summarizes product is of 3.73 mol of H2 produced per mols of methane
results from the process simulation of selected streams from being fed. Kang et al. [28] reported similar a yield in their
Fig. 1. simulation studies of the reduction of methane with Fe3O4,
In this Table, results from the extreme case where com- thus producing a yield of 2.64 mol of H2 per 1 mol of CH4.
plete production of CO2 is aimed (SIP) and the CH4/Fe3O4 feed However, this study was performed under thermally neutral
molar ratio is equal to 0.25 are presented. Here in this table conditions at 850  C with CO2 capture in the first reactor.
stream INPUT-1 denotes the fresh CH4 feed of 0.25 kmol/h, Moreover, Table 2 presents results from the simulation of
while the RECIRC stream contains 1 kmol/h of Fe3O4. Stream the CL-SMR process, which represents the other mode of
OUTPUT-1 contains the products from the fuel reactor at a operation described in Fig. 1. In this simulation a CH4/Fe3O4
temperature of 700  C where no carbon formation is possible feed molar ratio equal to 1 was employed in the fuel reactor.
and the complete oxidation of methane by magnetite is In this table stream INPUT-1 contains the fresh CH4 feed of
favored. In this stream, a methane conversion of 99.99% is 1 kmol/h, while the RECIRC stream contains also 1 kmol/h of
achieved with the production of 0.23 kmol/h of CO2 compared Fe3O4. Stream OUTPUT-1 comprises the products from the
to the theoretical 0.25 kmol/h according to reaction (5) making fuel reactor at a temperature of 700  C where no carbon for-
these operating conditions very convenient for carbon mation is possible and the complete oxidation of methane by
sequestration purposes, while the other carbon specie pro- magnetite is favored. In this stream a methane conversion of
duced is CO with 0.017 kmol/h accompanied with the pro- 90% is reflected with the production of 1.54 kmol/h of H2
duction of water. Furthermore, in this stream only 2.79 kmol/h compared to the theoretical 2 kmol/h according to reaction (9),
of FeO is generated, while only a small amount of unreacted while the production of CO was 0.7 kmol/h compared to the
Fe3O4 is present (0.068 kmol/h). Also, in this table the dry-basis theoretical value of 1 kmol/h of the same reaction. With
(DB) gas mol fractions in GASP-1 stream coming from the fuel respect to the reaction of the Fe3O4 with methane, it is

Table 1 e Summary of process simulation results of the SIP process.


Stream name INPUT1 RECIRC OUTPUT-1 GASP-1 INPUT2 STEAM OUTPUT-2 H2PROD
Mole flow, Kmol/h
CH4 0.25 0.00 0.00 0.00 0.00 0.000 0.00 0.00
CO 0.00 0.00 0.02 0.02 0.00 0.000 0.00 0.00
CO2 0.00 0.00 0.23 0.23 0.00 0.000 0.00 0.00
H2 0.00 0.00 0.05 0.05 0.00 0.000 0.93 0.93
H2O 0.00 0.00 0.45 0.45 0.00 6.000 5.07 5.07
Fe3O4 0.00 1.00 0.07 0.00 0.07 0.000 1.00 0.00
FeO 0.00 0.00 2.80 0.00 2.80 0.000 0.00 0.00
Fe 0.00 0.00 0.00 0.00 0.00 0.000 0.00 0.00
Mole Flow, Kmol/h 0.25 1.00 3.61 0.75 2.86 6.000 7.00 6.00
Mass Flow, Kg/h 4.01 231.54 235.55 18.92 216.63 108.092 324.72 93.18
Volume Flow, m3/h 20.38 0.04 61.17 61.12 0.05 429.69 429.82 429.78
Temperature,  C 720 600 720 720 720 600 600 600
Mol fractions (DB)
CH4 1 e 0.00 0.00 e e 0 0
CO 0 e 0.06 0.06 e e 0 0
CO2 0 e 0.77 0.77 e e 0 0
H2 0 e 0.17 0.17 e e 1 1

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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 x x x ( 2 0 1 7 ) 1 e1 3 11

Table 2 e Summary of process simulation results of the CL-SMR process.


Stream Name INPUT1 RECIRC OUTPUT-1 GASP-1 INPUT2 STEAM OUTPUT-2 H2PROD
Mole flow, Kmol/h
CH4 1.00 0.00 0.10 0.10 0.00 0.00 0.00 0.00
CO 0.00 0.00 0.70 0.70 0.00 0.00 0.00 0.00
CO2 0.00 0.00 0.20 0.20 0.00 0.00 0.00 0.00
H2 0.00 0.00 1.54 1.54 0.00 0.00 1.36 1.36
H 2O 0.00 0.00 0.26 0.26 0.00 8.20 6.84 6.84
Fe3O4 0.00 1.00 0.00 0.00 0.00 0.00 1.00 0.00
FeO 0.00 0.00 2.64 0.00 2.64 0.00 0.00 0.00
Fe 0.00 0.00 0.36 0.00 0.36 0.00 0.00 0.00
Mole Flow, Kmol/h 1.00 1.00 5.80 2.80 3.00 8.20 9.20 8.20
Mass Flow, Kg/h 16.04 231.54 247.58 37.78 209.80 147.73 357.53 125.99
Volume Flow, m3/h 81.52 0.04 223.66 223.61 0.05 587.25 587.42 587.37
Temperature,  C 720 600 700 700 700 600 600 600
Mol fractions (DB)
CH4 1 e 0.04 0.04 e e 0 0
CO 0 e 0.28 0.28 e e 0 0
CO2 0 e 0.08 0.08 e e 0 0
H2 0 e 0.61 0.61 e e 1 1

significant that two reduced iron species were produced with reducing conditions of the fuel reactor at temperatures greater
a combination of 2.64 and 0.36 kmol/h of FeO and Fe3O4, than 427  C, the presence of water-steam in the product
respectively. Here, it is possible that the syngas formed (which is the case of the present simulation results) contrib-
(H2 þ CO) is able to further reduce the FeO to a small extent. utes to a high instability of the carbide species.
Also in this Table, the dry-basis (DB) mol fractions of the In Fig. 2, coming from the fuel reactor, gases and solids are
product gas from the fuel reactor is presented. Here, mol separated in streams GASP-1 (syngas) and INPUT-2 (solid
fractions of 0.61 and 0.28 of H2 and CO, respectively were ob- product), where this last is fed to the oxidation reactor
tained with only small concentrations of unreacted methane together with stream STEAM, which according to results from
(0.04) and CO2 (0.08) being present. These results represent Table 2 consists of 8.2 kmol/h at a reactor temperature of
that reaction (9) is being dominant at this conditions. These 600  C. This excess of steam being fed at the oxidation reactor
results agree well with data reported by Kang et al. [28] who is needed to re-oxide FeO and Fe reduced species back to
found that in the case of the Fe oxide redox pairs at T ¼ 700  C, Fe3O4. Also, from Table 2 OUTPUT-2 stream contains the
Fe/Fe3O4 showed higher H2 mole fractions (0.649) than FeO/ products from the oxidation reactor where 1.36 kmol/h of H2
Fe3O4 (0.404), Fe0.947O/Fe3O4 (0.621) and Fe0.945O/Fe3O4 (0.444) combined with 1 kmol/h of Fe3O4 and 6.8 kmols/h of excess
showed higher H2 mole fractions than FeO/Fe3O4, even though steam. This stream is separated in H2PROD and RECIRC
FeO has a lower oxidation state than Fe0.947O and Fe0.945O. streams, where this last one is stent back to the fuel reactor.
Although wüstite has the ideal formula FeO, it is a non- The yield of this process based on the hydrogen product is
stoichiometric compound. Therefore, Fe0.945O and Fe0.947O 1.36 mol of H2 produced per 1 mol of methane being fed. While
are types of wüstite. Consequently, at a lower oxidation state based on the syngas produced is 2.24 mol of syngas (CO þ H2)
of the metal oxide the H2 mole fraction would be higher. per mol of methane fed along with a H2/CO molar ratio of 2.19.
Furthermore, Tong et al. [35] calculated the phase diagram of Go et al. [36] reported a synthetic gas (syngas) having the H2/
the iron oxidation states when subjected to varying partial (2CO þ 3CO2) molar ratio of 0.65, which is consistent with a
pressures of H2O/H2 and temperatures. At a given temperature value of 0.77 calculated from OUPUT-1 stream from results of
their phase diagram can describe the relationship between Table 2. Furthermore, the value of H2/CO ¼ 2.19 is very
iron oxide and fuel conversions where the operating line for convenient, since this streams can be used in the Fischer-
each mode of operation can be derived from an analytical Tropsch process for the production of liquid fuels (GTL).
oxygen balance between the gas and solid species in the
reducer reactor. According to their data at 600  C the corre-
sponding H2 mol fraction is of 0.62 (highly consistent with Conclusions
results found in the present research), while a maximum mol
fraction of 0.72 will indicate the formation of Fe, which the In the present research, the redox performance of iron oxide
present research aimed to avoid, since experimental results FeO/Fe3O4 redox pair as an oxygen carrier was investigated for
from Galvita and Sundmacher [30] reported that reduction hydrogen (H2) and/or syngas (H2þCO) production through a
towards Fe produced carbon deposits on the oxygen carrier. methane-steam redox process using a thermodynamic anal-
Moreover, no other chemical species were found during ysis and process simulation to find most favorable reactions
the equilibrium calculations such as iron carbides or carbon- conditions. The studied reaction system was divided in two
ates, which their content in the solid product from the reactors. In the fuel reactor the complete and/or partial
reducing reactor were negligible. This behavior agrees well oxidation of methane with Fe3O4 were studied. For the case
with findings from Svoboda et al. [30], who found that even where complete oxidation of CH4 along with production of
though iron carbide (Fe3C) is feasible to be formed under the CO2 and steam was aimed (SIP), optimal reaction conditions in

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Please cite this article in press as: Lo
process: Thermodynamic analysis, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.07.130
12 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 x x x ( 2 0 1 7 ) 1 e1 3

the first reactor include: a CH4/Fe3O4 molar feed of 0.25, remarkable stabilization of ceria-zirconia solution towards
T ¼ 700  C (with no carbon formation) and the complete CeAlO3 formation operated by Pt under redox conditions.
oxidation of CH4 by Fe3O4 with a methane conversion of Appl Catal B 2009;90:470e7.
[12] Sim A, Cant NW, Trimm DL. Ceria-zirconia stabilized
99.99%, producing 2.79 kmol/h of FeO. While optimal condi-
tungsten oxides for the production of hydrogen by the
tions in the second reactor comprise a steam feed of 6 kmol/h methane-water redox cycle. Int J Hydrogen Energy
and a reactor T ¼ 600  C, producing 0.93 kmol/h of H2 com- 2010;35:8953e61.
bined with 1 kmol/h of Fe3O4 and 5 kmols/h of excess steam. [13] Trovarelli A. Catalytic properties of ceria and CeO2-
The yield of this process (steam reactor) in molar basis was containing materials. Catal Rev Sci Eng 1996;38:439e520.
3.72H2 per CH4 feed. [14] Sosa Va zquez MI, Delgado Vigil MD, Salinas Gutie rrez J,
Collins-Martı́nez V, Lo pez Ortiz A. Synthesis gas production
For the case where the production of syngas was aimed in
through redox cycles of bimetallic oxides and methane. J
the fuel reactor, optimal reaction conditions include: a CH4/
New Mater Electrochem Syst 2009;12:29e34.
Fe3O4 molar feed of 1, T ¼ 700  C (with no carbon formation) [15] Zhu X, Wei Y, Wang H, Li K. CeeFe oxygen carriers for
and the partial oxidation of CH4 with small amounts of CO2 chemical-looping steam methane reforming. Int J Hydrogen
and unreacted CH4, along with 1 kmol/h of Fe3O4 with a Energy 2013;38:4492e501.
methane conversion of 90%. While optimal conditions in the [16] Zheng Y, Zhu X, Wang H, Li K, Wang Y, Wei Y. Characteristic
steam oxidation reactor comprise a steam feed of 8.20 kmol/h of macroporous CeO2-Zro2 oxygen carrier for chemical-
looping steam methane reforming. J Rare Earths
and a reactor T ¼ 600  C, producing 1.36 kmol/h of H2 com-
2014;32:842e8.
bined with 1 kmol/h of Fe3O4. The yield of this process (fuel
[17] Zhu X, Li K, Wei Y, Wang H, Sun L. Chemical-looping steam
reactor) in molar basis was 1.54 mol H2 per CH4 feed. methane reforming over a CeO2-Fe2O3 oxygen carrier:
Finally, these results can be taken as a basis for future evolution of its structure and reducibility. Energy Fuels
experimental and theoretical studies in search for a suitable 2014;28:754e60.
catalyst and experimental conditions to evaluate the present [18] Lee DH, Cha KS, Kim HS, Park CS, Kim YH. Syngas and
proposed technology. hydrogen production via stepwise methane reforming over
Cu-Ferrite/YSZ. Int J Energy Res 2014;38:1522e30.
[19] He F, Wei Y, Li H, Wang H. Synthesis gas generation by
references chemical-looping reforming using Ce-Based oxygen carriers
modified with Fe, Cu, and Mn oxides. Energy Fuels
2009;23:2095e102.
[1] Mueller-Langer F, Tzimas E, Kaltschmitt M, Peteves S. [20] Adanez J, Abad A, Garcia-Labiano F, Gayan P, De Diego LF.
Techno-economic assessment of hydrogen production Progress in chemical-looping combustion and
processes for the hydrogen economy for the short and reforming technologies. Prog Energy Combust Sci
medium term. Int J Hydrogen Energy 2007;32:3797e810. 2012;38:215e82.
[2] Markit HIS. Hydrogen. Chemical economics handbook. June [21] Mattisson T, Johansson M, Lyngfelt A. Multicycle reduction
2015. Available at: https://www.ihs.com/products/hydrogen- and oxidation of different types of iron oxide particles e
chemical-economics-handbook.html. application to chemical-looping combustion. Energy Fuels
[3] Yang J, Cai N, Li Z. Hydrogen production from the steam-iron 2004;18:628e37.
process with direct reduction of iron oxide by chemical [22] Mattisson T, Lyngfelt A, Cho P. The use of iron oxide as an
looping combustion of coal char. Energy Fuels oxygen carrier in chemical-looping combustion of methane
2008;22:2570e9. with inherent separation of CO2. Fuel 2001;80:1953e62.
[4] Bayham SC, Kim HR, Wang D, Tong A, Zeng L, McGiveron O, [23] Nasr S, Plucknett K. Kinetics of iron ore reduction by
et al. Iron-based coal direct chemical looping combustion methane for chemical looping combustion. Energy Fuels
process: 200-h continuous operation of a 25-kwth subpilot 2014;28:1387e95.
unit. Energy Fuels 2013;27:1347e56. [24] Cabello A, Abad A, Garcı́a-Labiano F, Gaya  n P, de Diego LF,
[5] Lee DH, Cha KS, Lee YS, Kang KS, Park CS, Kim YH. Effects of Ada nez J. Kinetic determination of a highly reactive
Ceo2 additive on redox characteristics of Fe-Based mixed impregnated Fe2O3/Al2O3 oxygen carrier for use in gas-fueled
oxide mediums for storage and production of hydrogen. Int J chemical looping combustion. Chem Eng J 2014;258:265e80.
Hydrogen Energy 2009;34:1417e22. [25] Monazam ER, Breault RW, Siriwardane R. Kinetics of
[6] Otsuka K, Kaburagi T, Yamada C, Takenaka S. Chemical magnetite (Fe3O4) oxidation to hematite (Fe2O3) in air for
storage of hydrogen by modified iron oxides. J Power Sources chemical looping combustion. Ind Eng Chem Res
2003;122:111e21. 2014;53:13320e8.
[7] Takenaka S, Hanaizumi N, Son VTD, Otsuka K. Production of [26] Fraser SD, Monsberger M, Hacker V. A thermodynamic
pure hydrogen from methane mediated by the redox of Ni- analysis of the reformer sponge iron cycle. J Power Sources
and Cr-Added iron oxides. J Catal 2004;228:405e16. 2006;161:420e43.
[8] Urasaki K, Tanimoto N, Hayashi T, Sekine Y, Kikuchi E, [27] Steinfeld A, Kuhn P. High-temperature solar
Matsukata M. Hydrogen production via steam-iron reaction thermochemistry: production of iron and synthesis gas by
using iron oxide modified with very small amounts of Fe3O4-reduction with methane. Energy 1993;18:239e49.
palladium and zirconia. Appl Catal A 2005;288:143e8. [28] Kang K, Kim C, Bae K, Cho W, Kim S, Park C. Oxygen-carrier
[9] Zafar Q, Mattisson T, Gevert B. Redox investigation of some selection and thermal analysis of the chemical-looping
oxides of transition-state metals Ni, Cu, Fe, and Mn process for hydrogen production. Int J Hydrogen Energy
supported on Sio2 and MgAl2O4. Energy Fuels 2006;20:34e44. 2010;35:12246e54.
[10] Galvita V, Sundmacher K. Cyclic water gas shift reactor [29] Bohn CD, Muller CR, Cleeton JP, Hayhurst AN, Davidson JF,
(CWGS) for carbon monoxide removal from hydrogen feed Scott SA, et al. Production of very pure hydrogen with
gas for PEM fuel cells. Chem Eng J 2007;134:168e74. simultaneous capture of carbon dioxide using the redox
[11] Liotta LF, Longo A, Pantaleo G, Di Carlo G, Martorana A, reactions of iron oxides in packed beds. Ind Eng Chem Res
Cimino S. Alumina supported Pt (1%)/Ce0.6Zr0.4O2 monolith: 2008;47:7623e30.

 pez-Ortiz A, et al., Hydrogen production by a Fe-based oxygen carrier and methane-steam redox
Please cite this article in press as: Lo
process: Thermodynamic analysis, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.07.130
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 x x x ( 2 0 1 7 ) 1 e1 3 13

[30] Svoboda K, Slowinski G, Rogut J, Baxter D. Thermodynamic steam cyclic redox processes with iron-based metal oxides.
possibilities and constraints for pure hydrogen production by Int J Hydrogen Energy 2011;36:6646e56.
iron based chemical looping process at lower temperatures. [34] Tang M, Xu L, Fan M. Progress in oxygen carrier development
Energy Convers Manag 2007;48:3063e73. of methane-based chemical-looping reforming: a review.
[31] Galvita V, Sundmacher K. Hydrogen production from Appl Energy 2015;15:1143e56.
methane by steam reforming in a periodically operated two- [35] Tong A, Bayham S, Kathe MV, Zeng L, Luo S, Fan L. Iron-
layer catalytic reactor. Appl Catal A 2005;289:121e7. based syngas chemical looping process and coal-direct
[32] Collins-Martı́nez V, Escobedo Bretado M, Mele ndez chemical looping process development at Ohio State
Zaragoza M, Salinas Gutie rrez J, Lo
 pez Ortiz A. Absorption University. Appl Energy 2014;113:1836e45.
enhanced reforming of light alcohols (methanol and ethanol) [36] Go KS, Son SR, Kim SD, Kang KS, Park CS. Hydrogen
for the production of hydrogen: thermodynamic modeling. production from two-step steam methane reforming in
Int J Hydrogen Energy 2013;38:12539e53. a fluidized bed reactor. Int J Hydrogen Energy
[33] Yamaguchi D, Tang L, Wonga L, Burke N, Trimm D, 2009;34:1301e9.
Nguyen K, et al. Hydrogen production through methane-

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