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 3 7 ( 2 0 1 2 ) 7 4 4 2 e7 4 5 0

Available online at www.sciencedirect.com

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

Production of hydrogen via an Iron/Iron oxide looping cycle:

Thermodynamic modeling and experimental validation
A. Singh, F. Al-Raqom, J. Klausner, J. Petrasch*
Department of Mechanical and Aerospace Engineering, University of Florida, Gainesville, FL 32611, USA

article info

abstract

Article history:

An incremental thermodynamic equilibrium model has been developed for the chemical

Received 8 November 2011

reactions driving a clean, hydrogen producing iron/iron oxide looping cycle. The model

Received in revised form

approximates a well-mixed reactor with continuous reactant gas flow through a stationary

18 January 2012

solid matrix, where the gas residence time is long compared to time constants associated

Accepted 19 January 2012

with chemical kinetics and species transport. The model, which computes the theoretical

Available online 23 February 2012

limit for steam-to-hydrogen conversion, has been experimentally validated for the
oxidation reaction using an externally heated, 21 mm inner diameter, tubular fluidized bed

Keywords:

reactor. Experiments were carried out at 660 and 960
C with steam flow rates ranging from

Looping cycle

0.9 to 3.5 g/min. For small flow rates, i.e., for long residence times, the experimentally

Hydrogen

observed cumulative steam-to-hydrogen conversion approaches the theoretically pre

C operating temperature, the measured hydrogen yield

Iron oxide

dicted conversion. At a 960

Thermochemical

approaches the theoretical limit (experimental yields are always within 50% of the theo-

Syngas

retical limit), and the yield is insensitive to variations in the steam flow rate. In contrast,

Coal

the measured hydrogen yield deviates significantly from the theoretical limit at a 660
C
operating temperature, and strong variations in hydrogen yield are observed with variations in steam flow rate. This observation suggests that the reaction kinetics are significantly slower at lower temperature, and the model assumption is not satisfied.
Copyright 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1.

Introduction

The solar thermochemical production of fuels such as

hydrogen or Syngas using metal/metal oxide looping
processes [1e3] is considered an interesting route to carbonneutral fuels. The concept shows promise in helping to
satisfy a growing global energy demand, reducing oil price
volatility, and mitigating anthropogenic climate change. Solar
driven looping processes use water and CO2 as the sole feedstocks and concentrated solar radiation as the sole energy
source. Looping processes using natural gas [4e7] or coal-

derived Syngas [8,9] as the reducing agent constitute an

important stepping-stone toward carbon-neutral hydrogen
production. This study uses iron/iron oxide redox pairs as the
reactive material [10]. This process is capable of producing
significantly higher purity hydrogen than conventional coal
gasification and subsequent water gas shift [11,12]. Another
advantage is that the process avoids gas-phase separation.
Metallic iron is oxidized by steam, producing hydrogen and
iron oxides during the first reaction step. Coal-derived Syngas
is then passed through the oxides, reducing them back to iron
during the second reaction step. Since the gaseous products of

* Corresponding author. University of Florida, Department of Mechanical and Aerospace Engineering, 330 MAE-B, Gainesville, FL 32611,
USA. Tel.: 1 352 392 9129.
E-mail address: joerg.petrasch@fhv.at (J. Petrasch).
0360-3199/$ e see front matter Copyright 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2012.01.074

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Nomenclature
cp
G
g0i
h
_
m
M
mFe
P

1

1

Specific heat capacity, kJ kmol K

Gibbs free energy, kJ
Reference Gibbs function of species i evaluated,
kJ kmol1
Enthalpy, kJ kmol1
Mass flow rate, kg s1
Molar mass, kg kmol1
Mass of iron, kg
Total system pressure, N m2

the oxidation reaction consist of hydrogen and steam only,

the process can generate highly pure hydrogen through steam
condensation. Furthermore the reduction step yields highly
concentrated CO2 suitable for sequestration.
The suggested two-step process uses the same reactor for
both the reduction and the oxidation reaction. The solid
reactants remain in the reactor and streams of steam and
Syngas are alternatingly fed to the reactors [9]. In contrast, the
three-step steam-iron process [6,11e20] employs two separate
reactors for hydrogen production and iron oxide reduction
[21], hence necessitating the transport of hot solids between
reactors.
To evaluate the theoretical potential of the suggested twostep process, an open system incremental thermodynamic
equilibrium model is developed for both the hydrogen
production (oxidation) step and the regeneration (reduction)
step. The hydrogen production step is also carried out experimentally to study the validity of the thermodynamic model
and to determine the conditions for its applicability. Roeb
et al. [22] conducted a thermodynamic analysis for two-step
water splitting with mixed iron oxides including nickel-ironoxide and zinc-iron-oxide to evaluate the maximum
hydrogen production potential of coating materials using
FactSage software [23]. Their analysis showed that maximum
hydrogen yield is realized when (i) the reduction temperature
is raised to 1300
C, (ii) the water splitting temperature is
lowered below 800
C, and (iii) the oxygen partial pressure
during reduction is minimized. This is consistent with similar
findings by Singh et al. [9]. Roeb et al. have also validated the
effect of reduction temperature and oxygen partial pressure in
experimental studies. However, they could not experimentally verify the increased hydrogen yield at lower water
splitting temperatures of approximately 800
C. They
concluded that kinetics play an important role in the oxidation step. Svoboda et al., have carried out a thermodynamic
study of the potentials and limitations of iron based chemical
looping processes for the production of high purity hydrogen.
They studied the FeeFe3O4 system for cyclic hydrogen
production in the temperature range of 400e800 K [8]. In their
analysis, they have evaluated the hydrogen yield at equilibrium for the steam oxidation of pure iron to magnetite (Fe3O4).
In accordance with Singh et al. and Roeb et al., [9,22] their
theoretical results showed that lower oxidation temperatures
are favorable for attaining higher hydrogen yields. They have
also indicated that at lower temperatures, the reaction is
limited by kinetics.

ni
mFe,init
Pref
PID
R
sLPM
T
t
yi,eq
yi

7443

Number of moles for a species i, kmol

Initial mass of iron, kg
Reference pressure, N m2
Proportional-integral-derivative
Universal gas constant, kJ kmol1 K1
Standard liters per minute
Temperature, K
time, s
Mole fraction at equilibrium
Species i mole fraction

In the current study, an incremental thermodynamic

equilibrium model is employed to predict the maximum
attainable reaction yields. The model approximates a wellmixed reactor with continuous reactant gas flow through
a stationary solid matrix where the gas residence time is long
compared to time constants associated with chemical
kinetics. The model is validated experimentally for the
oxidation case using an externally heated tubular fluidized
bed reactor. The current study is limited to the oxidation
reaction of the looping cycle.

2.

Thermodynamic analysis

The ideal two-step iron based looping process for the

production of hydrogen consists of the hydrogen production
step [2]:
Fe 4=3 H2 O/1=3Fe3 O4 4=3H2 ;
Dh 31:75 kJ=mol at 960
C;

(1)

followed by the reduction step:

1=3Fe3 O4 2=3CO 2=3H2 /Fe 2=3CO2 2=3H2 O;
Dh 1:25 kJ=mol at 960
C:

(2)

High purity hydrogen and magnetite are produced during

the first step. During the second step, magnetite is reduced
back to iron using Syngas as the reducing agent. Coking and
iron carbide formation may occur during reduction. These
products may react with steam in the oxidation process
producing CO, CO2, and CH4 along with hydrogen. A detailed
analysis of the by-products of the reduction reaction has
been carried out in [9]. In the ideal process hydrogen is
completely consumed in the reduction reaction. However, in
real processes a large fraction of the hydrogen will not react.
The hydrogen and CO2 in the off-gases of the reduction step
may be separated via conventional techniques, such as
pressure swing absorption (PSA) [25] leading to lower purity
hydrogen.
An open system equilibrium model (Fig. 1) for a single
looping reactor is implemented. Small amounts of steam are
added to the system and the ensuing equilibrium reactant gas
mixture is removed from the system. Solid material remains
within the system. Assuming constant temperature and
pressure and ideal gas behavior, the species balance for
a gaseous component follows:

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Fig. 1 e Equilibrium reactor diagram.



dyi;gas
n_ yi;gas;in  yi;gas;eq ngas ; nsolid ; T; P
dt


yi;solid yi;solid;eq ngas ; nsolid ; T; p

(3)

Species considered in the thermodynamic reactor models

are H2, H2O, CH4, C, CO, CO2, Fe, FeO, Fe3O4, Fe2O3, FeCO3, O2,
and Fe3C. Equilibrium compositions for the open system
oxidation/reduction process are calculated using Gibbs free
energy minimization,




yi;gas=solid;eq ngas ; nsolid ; T; p arg min G ngas ; nsolid ; T; P
ngas ;nsolid

Fig. 2 e Conceptual looping plant layout.

(4)

where


ngas n1;gas ; n2;gas ; .; nn;gas


nsolid n1;solid ; n2;solid ; .; nm;solid
ni;gas
ni;solid
yi;gas Pn
; yi;solid Pn
i1 ni;gas
i1 ni;solid

(5)

The Gibbs free energy is calculated assuming two separate

phases in close contact, namely a mixture of ideal gases, and
a perfectly mixed incompressible solid.
G

Xn
i1

Gi;gas

Xm
i1

Gi;solid



Gi;gas ni g0i ni RT ln yi P=Pref ; Gi;solid ni g0i ni RT ln yi

(6)
(7)

The number of moles of all species, ni,gas and ni,solid is constrained such that the elemental balance of the total system is
satisfied. Reference values for enthalpy, entropy, and the
temperature dependent specific heat, cp, have been obtained
from the HSC 7.0 database [24].
A steady state model, coded in Matlab [26], has been
developed for the conceptual looping plant layout shown in
Fig. 2; the model features open system chemical equilibrium
analysis, heat and mass balance on the reactors, and heat and
mass balance on the heat exchangers. The model is used to
predict reactor yields and identify the amount of reactant
gases necessary to achieve satisfactory conversion. Analyses
have been carried out for the temperature range between 27
C
and 960
C, at an operating pressure of 1 bar [9].

2.1.

Experimental facility

A bench scale experimental facility featuring a 21 mm inner

diameter tubular fluidized bed reactor for the iron/iron oxide
hydrogen production looping process has been fabricated. A
pictorial view of the hydrogen production experimental
facility is shown in Fig. 3 and a corresponding flow diagram is
shown in Fig. 4. The facility includes a 21 mm inner diameter,
0.6 m long fused quartz tube. Fused quartz is a non-crystalline
form of silica with a melting point of 1665
C [27]. To prevent

powder carry-over, a 20 mm pore size stainless steel frit is

inserted at the top of the tube as depicted in reactor diagram
(Fig. 5). The powder is placed on a distributor made of
a Cotronics ceramic blanket thermal insulation material that
can withstand a temperature up to 1650
C [28]. The tube ends
are sealed with stainless steel fittings using silicon O-rings
that can withstand temperatures up to 300
C. The quartz tube
reactor extends through an MTI electric furnace. The furnace
has a continuous operational range of 100e1000
C and can
operate at 1100
C for a short time span (less than 2 h). The
furnace has a heating rate of 20
C /min. It is equipped with
a PID controller and features 30 programmable segments (/
1
C accuracy) [29]. The length of the furnace heating zone is
300 mm with a constant temperature zone length of 80 mm. A
K-type thermocouple is placed near the center of the furnace.
A steam generator consisting of four 200 W cartridge heaters
inside an aluminum chamber is used to generate vapor.
Stainless steel wool and a stainless steel screen are inserted in
the aluminum chamber to separate out water droplets and to
ensure dry steam discharges the steam generator. The steam
generator is thermally insulated with fiber glass insulation.
The rate of steam generation is controlled with a pulse-width
modulated signal (PMS) and solid-state relay at a frequency of
2 Hz. A 120 VAC power source provides power to the steam
generator. The steam is superheated to about 200
C by
passing it through an Omega Engineering, 1.37 cm outer
diameter (0.2500 NPT) 200 W in-line gas heater [30] that is
mounted vertically and is capable of heating gas from an inlet
temperature of 121
C up to 540
C with a maximum gas
volumetric flow rate of 0.227 m3/min (8 CFM). Two water
cooled condensers are used. One condenser is used to determine the steam mass flow rate based on the volume of
condensate collected in a separate steady state measurement
prior to the experiment. The other condenser is used to
remove excess water from the hydrogen/steam mixture flow
discharging the reactor. The condensed water is accumulated
in a water trap and the weight of the water accumulated is
used to determine the amount of unreacted steam. The
volume of the produced hydrogen is determined by visual

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 3 7 ( 2 0 1 2 ) 7 4 4 2 e7 4 5 0

Fig. 3 e Pictorial view of hydrogen production experimental facility.

Fig. 4 e Flow diagram of hydrogen production experimental facility.

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Table 1 e WD experiment operating conditions.

Experiment #
1
2
3
4
5
6

Steam mass flow

rate (g/min)
3.5
1.9
0.9
3.5
0.9
1.9

 0.2
 0.1
 0.1
 0.2
 0.1
 0.1

Bed Ta (
C)
956  7
962  7
950  7
641  5
681  5
693  5

a The temperature error for k-type thermocouples is estimated to

be 0.75% of the measured temperature [34].

Fig. 5 e Schematic depiction of electrical furnace and

tubular reactor.

inspection of water displacement in an inverted graduated

cylinder at normal conditions (NTP, 20
C and 101 kPa). The
inverted graduated glass cylinders with 2000 ml capacity are
immersed in a water bath. Stainless steel sheathed E-type and
J-type thermocouples are used to monitor and record the gas
temperatures entering and exiting the tube reactor as well as
the temperatures of the fittings. A K-type thermocouple is
used to monitor the bed temperature. A National Instruments
data acquisition board, NI USAB-6225 [31], is used to collect
the thermocouple and flow meter voltage signals. A Labview
virtual instrument is used to observe, control and collect the
experimental data.

2.2.

powder are used. The powder is mixed with 99.5% pure silica
in a 2:1 silica to iron volume ratio to retard sintering. The silica
(SIL-CO-SIL 63, U.S. Silica) sieve analysis is also illustrated in
Fig. 6 [33]. The mixed iron/silica bed is placed on the distributor in the quartz tube, which is then sealed with stainless
steel fittings. The quartz tube extends outside the electrical
furnace. The bottom portion of the quartz tube is insulated
with a ceramic blanket that is held in place with stainless steel
bands to prevent steam condensation. A nitrogen flow is
passed through the reactor with a volumetric flow rate of 2
sLPM to heat the system to at least 150
C and to purge the air
in the system, thus preventing oxidation of the iron powder.
In industrial practice, no nitrogen will be used, discharge gas
will be recirculates through the reactors. Using a three-way
valve, the steam is either directed to a condenser, which
empties into a graduated cylinder, or the steam is directed to
the reaction chamber. The mass flow rate of steam is
controlled via the heat input to the boiler. The exact steam
mass flow rate is determined by measuring the rate of
condensate when steam is directed to the condenser prior to
the actual experiment. The electrical furnace temperature is
set for the desired reaction temperature and held at the
temperature for the duration of the experiment. Once the
stainless steel fitting temperatures reach 150
C and the steam
flow rate reaches steady state, the nitrogen is shut off, and the
steam is directed into the gas heater section, where it is
superheated and then directed to the reactor. Hydrogen and
excess steam leave the reactor and pass through a condenser
upon initiation of the oxidation reaction. The condensed
water is collected in a sealed cylinder (water trap). After the

Description of experiments

Experiments are carried out to evaluate the water dissociation

(WD) step in the Iron/Iron oxide looping cycle. Reactor bed
temperatures of 660 and 960
C and steam mass flow rates of
0.9, 1.9, and 3.5 g/min are considered. Table 1 lists the operating conditions for the six WD experiments. The total duration of the WD experiments ranges between 35 and 50 min.
High purity Ancor MH-100 porous iron powder with 99.56%
purity manufactured by Hoeganaes Corporation is used [32].
The iron is a porous powder with an average apparent density
of 2.5 g/cm3, a material density of 7.87 g/cm3 and a melting
point of 1536
C. Results of the iron powder sieve analysis are
shown in Fig. 6. In each experiment approximately 25 g of iron

Fig. 6 e Iron and silica powder size distributions by weight.

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 3 7 ( 2 0 1 2 ) 7 4 4 2 e7 4 5 0

7447

Table 2 e Uncertainty in steam mass flow rate

measurements.
Steam mass flow rate (g/min)

Uncertainty (g/min)

3.5
1.9
0.9

0.2
0.1
0.1

removal of all excess water, pure hydrogen is directed into an

inverted water-filled, graduated cylinder. The accumulated
amount of hydrogen is determined by visual observation of
the water displaced from the graduated cylinders.

2.3.

Error analysis

An error analysis is used to assess the measurement uncertainty. The steam mass flow rate is determined from the rate
of the steam condensate accumulation. The measurements
are repeated, and the standard deviation (s) is used as
a statistical measure of the absolute error. The measurement
uncertainty is taken as s. For each operating condition, the
steam mass flow rate is measured twice. The standard deviation for the steam mass flow rate error is listed in Table 2.
The volumetric hydrogen yield is determined by measuring
the displaced water volume in an inverted graduated cylinder.
The uncertainty associated with the measurement involves
a visual inspection of the water meniscus. The water
meniscus reading is affected by the disruption of hydrogen
bubbles rising through the inverted cylinder. These disruptions are more frequent at higher rates of reaction. The
measurement uncertainty and relative error (error in
meniscus reading) are estimated and listed in Table 3.

3.

Results and discussion

The measured hydrogen yields using the fluidized bed of iron

particles at different steam flow rates are compared to the

Fig. 7 e The Open system hydrogen production at 660
C

for flow rates of 0.9, 1.9, and 3.5 g/min.

theoretical open system incremental equilibrium yield at bed

temperatures of 660 and 960
C. Figs. 7 and 8 show the
hydrogen yield as a function of the cumulative steam fed to
the reactor for the 660 and 960
C respective bed temperatures.
The abscissa shows the ratio of the cumulative steam mass
flowing into the reactor to the stoichiometric steam mass
necessary for complete conversion of Fe to Fe3O4,
PH2 O

_ H2 O $t
m
4 MH2 O
mFe;initial
3 MFe

(8)

The ordinate shows the ratio of the cumulative hydrogen

mass discharging the reactor to the stoichiometric mass of
hydrogen that can be produced from complete conversion
from Fe to Fe3O4,
PH2

_ H2 $t
m
4 MH2
mFe;initial
3 MFe

(9)

Table 3 e Hydrogen yield measurement uncertainty and

relative error.
T (
C)

660

_ H2 O
m
(kg/min)

t
(min)

3.5

0e15
15etfinal
0e15
15etfinal
0e15
15etfinal
0e6
6e20
20etfinal
0e20
20etfinal
0e20
20etfinal

1.9
0.9
960

3.5

1.9
0.9

Uncertainty
H2
Relative
(ml)
volume error (%)
(ml)
10
5
5
1
5
1
20
10
5
10
5
5
1

200
200
200
200
200
200
200
200
200
200
200
200
200

5.0
2.5
2.5
0.5
2.5
0.5
10.0
5.0
2.5
5.0
2.5
2.5
0.5

Fig. 8 e The Open system hydrogen production at 960
C

for flow rates of 0.9, 1.9, and 3.5 g/min.

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Fig. 9 e The open system solid molar composition for the

hydrogen production step at 660
C.

Fig. 11 e Predicted total mass of the solid phase for

hydrogen production step at 660
C.

Fig. 7 shows that hydrogen yield increases with decreasing

flow rate (increasing residence time) and moves toward the
thermodynamic limit with increasing cumulative mass of
steam entering the reactor. The influence of slow reaction
kinetics at lower temperatures is clearly discernible. In Fig. 8,
the hydrogen production rate is observed to be relatively
insensitive to the steam flow rate because reaction kinetics are
enhanced at higher temperatures. The thermodynamic limit is
approached, particularly at high cumulative steam throughput.
The cumulative steam throughput is quite important since
there is an energy cost for water to steam conversion.
The sharp bends in the theoretical yield curves are associated with completion of the oxidation of metallic iron and
the completion of oxidation of FeO respectively (see also Figs.
9 and 10). Most of the theoretical steam-to-hydrogen conversion occurs with small cumulative amounts of steam. This
allows for high theoretical energy efficiencies, since little
excess steam needs to be produced. However, even at high
temperatures, experiments do not match the steep initial rise

in cumulative H2 production. The experimental curves also do

not exhibit the two sharp bends. This is due to non uniform
mixing of the solid phase.
Figs. 9 and 10 show the variation of the theoretical solid
phase composition as a function of the cumulative amount of
steam employed for the 660 and 960
C respective bed
temperatures. At higher temperature (960
C) relatively more
Fe3O4 and Fe2O3 are formed. A small amount of elemental Fe
persist at the 960
C bed temperature.
Figs. 11 and 12 show the total solid phase mass normalized
by the initial iron mass as a function of the cumulative mass of
steam into the reactor for the 660 and 960
C respective bed
temperatures. Both the theoretical limit of solid phase mass
and that inferred from experimental hydrogen production
data via a gas-phase mass balance are shown. In both figures,
the large symbols at the end of the experimental curves denote
the final mass determined via weighing at the end of the
experiment. The discrepancy is attributed to the breakdown of
Fe-particles swept away during the experiment as well as
incomplete extraction of the solid phase after the experiment.

Fig. 10 e The open system solid molar composition for the

hydrogen production step at 960
C.

Fig. 12 e Predicted total mass of the solid phase for

hydrogen production step at 960
C.

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 3 7 ( 2 0 1 2 ) 7 4 4 2 e7 4 5 0

4.

Conclusions

Hydrogen production via the iron/iron oxide looping cycle has

been studied theoretically and experimentally. An incremental thermodynamic equilibrium open system model has
been developed. The model has been used to predict hydrogen
yields, and solid compositions for the oxidation step and offgas as well as solid composition for the reduction step.
Theoretical predictions have been experimentally validated
for the hydrogen production step at 660 and 960
C for steam
flow rates between 0.9 and 3.5 g/min. As the steam flow rate to
the reactor decreases, i.e., as the residence time of steam in
the reactor increases, the experimentally observed cumulative steam-to-hydrogen conversion approaches the theoretically predicted values. The steep initial rise of the theoretical
yield shows the potential for efficient conversion of steam-tohydrogen. However, particularly at low temperatures and
during the initial reaction phase, experimental yields remain
significantly below the theoretical limit. Increasing the residence time partially alleviates these issues. At higher
temperatures reduction of the flow rate (i.e., increasing the
residence time) has only a marginal effect on conversion,
indicating very slow effective kinetics beyond a certain
Hydrogen yield. This is consistent with ongoing kinetic
modeling in which two distinct kinetic regimes, (i) a shrinking
sphere regime, and (ii) a diffusion-limited regime, has been
identified. Based on this study it is concluded that the diffusion-limited regime proves a severe obstacle to efficient
reactor operation and should be avoided. A combination of
measures is suggested to overcome these obstacles: (i) minimize the particle size as far as possible without unacceptable
mass losses to maximize the surface to volume ratio, (ii)
increase the gas-phase residence time, e.g., via recirculation,
and (iii) only partially reduce and oxidize the iron based
reactants to avoid the diffusion-limited regime.

Acknowledgments
Financial support for this study by the United States Department of Energy under Award No. DE-FE0001321 is gratefully
acknowledged.

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