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Solar Energy 125 (2016) 339–359
www.elsevier.com/locate/solener

Receiver reactor concept and model development for a solar

steam redox reformer
Elysia J. Sheu, Ahmed F. Ghoniem ⇑
Department of Mechanical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA, USA

Received 7 September 2015; received in revised form 4 December 2015; accepted 14 December 2015
Available online 8 January 2016

Communicated by: Associate Editor Michael Epstein

Abstract

As concern over the CO2 emissions associated with power production from traditional fossil fuels grows, there has been more interest
in using renewable energy sources such as solar energy. However, there are many issues with using solar energy on a large scale including
dispatchability and economically viable storage methods. A potential solution to these problems is using a hybrid solar-fossil fuel power
generation system. Within such systems, solar reforming has been shown to be a promising integration method with steam redox reform-
ing as an effective reforming process. In this article, a receiver reactor concept for a solar steam redox reformer is presented. The receiver-
reactor consists of a dumbbell shape absorber system that has two distinct absorbers. This absorber system setup allows for the switching
between reduction and oxidation steps without having to constantly change inlet streams to the reactor and is designed such that the inlet
connections do not interfere with the solar window. In addition, at any point in time only one solar absorber is irradiated by the solar
energy (during the reduction step). A computational model is developed to assess its performance. Simulations show that the receiver-
reactor strongly absorbs the solar radiation and most of the radiative heat transfer occurs in the front half of the reactor. Moreover,
results show that higher conductivity absorber materials yield smaller temperature variations not only within the reactor but also with
time, and therefore are more suitable for long term reactor operation.
Ó 2015 Elsevier Ltd. All rights reserved.

Keywords: Hybrid solar-fossil fuel; Solar reforming; Steam redox

1. Introduction economically viable methods of storage as well as intermit-

There has been much interest in the use of renewable
energy resources such as solar energy for power generation
as means for limiting CO2 emissions associated with power
production from fossil fuels. However, currently and for
near term projections, only a small percentage of the
world’s power production comes from non-hydropower
renewables (International Energy Outlook, 2013). The
reasons for this small percentage include the lack of
⇑ Corresponding author. Tel.: +1 6172532295; fax: +1 6172535981.
E-mail address: ghoniem@mit.edu (A.F. Ghoniem).
tency and dispatchability problems with renewable power
sources like solar energy. One potential solution to this
problem is the use of hybrid solar fossil fuel power gener-
ation. In this hybrid operation, there is the potential to
reduce emissions as compared to fossil fuel only power pro-
duction while avoiding the intermittency problems associ-
ated with solar only power production. Within this scope
of hybrid solar fossil fuel power generation, there are a
number of ways in which the solar energy can be incorpo-
rated into a fossil fuel power cycle (Sheu et al., 2012), and
previous work has shown that solar reforming is a promis-
ing integration method (Sheu and Mitsos, 2013).

http://dx.doi.org/10.1016/j.solener.2015.12.024
0038-092X/Ó 2015 Elsevier Ltd. All rights reserved.
340 E.J. Sheu, A.F. Ghoniem / Solar Energy 125 (2016) 339–359
Nomenclature
Latin letters
u velocity (m/s)
T temperature (K)
ks thermal conductivity (W/m/K)
K ext extinction coefficient (m1)
d channel size (m)
L channel length (m)
The solar reforming integration method involves
reforming the fuel (natural gas) into syngas (which has a
higher heating value) using solar energy. The syngas is then
used as a fuel for the gas turbine to produce power in a
combined cycle. Solar reformers can be categorized into
two main categories: directly irradiated and indirectly irra-
diated. In this work, the focus will be on directly irradiated
solar reformers as higher temperatures can be reached in
these reformers which leads to higher methane conversion.
However, it should be noted that indirectly irradiated
reformers can also be of great interest due to cost consider-
ations. For a directly irradiated solar reformer, the solar
receiver and reactor are one integrated unit. In traditional
solar receivers used in solar only power production, a solar
absorber (usually a porous ceramic disk or wire mesh) is
placed inside a solar receiver and irradiated by the solar
energy. A heat transfer fluid is then sent through the solar
absorber and heated by convection. To apply this concept
to solar reforming, the solar absorber merely becomes the
reaction site. Most often in these solar reformers, the solar
absorber is a porous ceramic disk or ceramic honeycomb
with any catalyst needed for the reforming process coated
onto the porous surface or channels. The most commonly
used solar reforming processes are steam reforming, dry
reforming, and redox reforming. There has been much
experimental work with steam and dry solar reformers
(Anikeev et al., 1998; Berman et al., 2007; Buck et al.,
1991; Maria et al., 1986; Dahl et al., 2004; Levy et al.,
1992; Wörner and Tamme, 1998), and to a less extent on
redox solar reformers as well (Kodama et al., 2000;
Steinfeld et al., 1998; Steinfeld et al., 1993). Meanwhile
there has been much less computational work, with only
a few numerical studies on steam and dry solar reformers
(Ben-Zvi and Karni, 2007; Petrasch and Steinfeld, 2007;
Skocypec et al., 1994). Development of computational
models for solar reformers in conjunction with experimen-
tal studies can aid in the design and operation of the solar
reformer for use in hybrid solar fossil fuel power
production.
Previous system analysis has shown that steam redox
reforming has some advantages for use in hybrid power
cycles (Sheu and Ghoniem, 2014) and will be the focus in
this work. Moreover, since a number of different oxygen
Greek symbols
 porosity
rs scattering coefficient (m1)
ra absorption coefficient (m1)
d thickness (m)
gCH 4 methane conversion
gsu solar utilization efficiency
carriers can be used, redox reforming does not require
the use of expensive noble metal catalysts (as is usually
the case with solar dry and steam reformers). Steam redox
reforming can also yield product compositions with more
desirable H2/CO ratios than direct steam reforming. In this
article, a design for a receiver-reactor that can be used for
the steam redox process is discussed. In addition, a compu-
tational model that can aid in the design of the solar reac-
tor is presented. Finally, a set of base case results from the
reactor model is shown and the validity of the results
discussed.
2. Receiver–reactor design
As mentioned previously, the solar reformer studied
herein uses steam redox reforming which consists of two
main reactions: a (metal) reduction reaction and an oxida-
tion reaction. In previous work, iron oxide has been shown
to be a promising option as an oxygen carrier for a steam
redox reformer and hence is utilized in this analysis (Sheu
and Ghoniem, 2014). For this reformer, the two states
for the oxygen carrier are magnetite (Fe3O4) and wustite
(FeO). Thus, the two main reactions for the reformer stud-
ied herein are
Reduction : CH4 þ Fe3 O4 ! 3FeO þ CO þ 2H2
DH ¼ 266:60 kJ=mol
o
Oxidation : 3FeO þ H2 O ! Fe3 O4 þ H2
DH ¼ 60:44 kJ=mol
o
Note that CO2 can also be used as the oxidizing agent.
However, steam is used in this analysis due to the faster
oxidation rates (Stehle et al., 2011).
In chemical looping applications, often times two sepa-
rate reactors are used (one for oxidation and one for reduc-
tion) with a fluidized bed circulating the oxygen carrier
between the two reactors (Adanez et al., 2012). However,
the energy required for the circulating bed as well as the
associated pressure drop can be detrimental to reformer per-
formance (Adanez et al., 2012). Moreover, there are other
complexities associated with maintaining the fluidized bed,
separating the particles, and particle agglomeration at high
temperatures (Adanez et al., 2012). Therefore, the reactor
 E.J. Sheu, A.F. Ghoniem / Solar Energy 125 (2016) 339–359
design proposed here is one where the reaction site is the
solar absorber which has the oxygen carrier coated on to
it (similar to what is commonly used in direct dry and steam
solar reformers). The solar absorber used in this reactor is a
honeycomb ‘‘disk” with micro-channels, as this type has
been shown to be advantageous in terms of fuel conversion
and more even temperature distribution (Levy et al., 1992).
A schematic of how the reactor is incorporated with the
solar collector is shown in Fig. 1. Note that in the schematic
the reactor is shown with a dish solar collector/receiver sys-
tem; however, the reactor could also be implemented with a
solar tower type receiver as well.
Unlike more traditional steam and dry reformers, the
steam redox process is a two step process and therefore
requires some sort of switching mechanism in order to go
between the reduction and oxidation processes. One way
of achieving this is to switch the inlet streams going into
the reactor between the reducing and oxidizing agent. How-
ever, the control and execution of this inlet stream switching
can be quite difficult in terms of implementation. Thus, for
this reactor design, the solar absorber itself is the compo-
nent that is moving and switching between the two reform-
ing steps. Essentially, this reactor has two solar absorbers
which switch between the two inlet ports that have constant
flow of the reducing and oxidizing agent. Moreover, in this
reactor design, the solar energy is only used during the
reduction step as this step is highly endothermic while the
oxidation step is slightly exothermic. Thus at any point in
time, only one of the solar absorbers will be irradiated by
the solar radiation. Schematics of the reactor design for this
switching reactor are shown in Fig. 2.
The two absorber system in the reactor is essentially a
dumbbell shape. For a certain cycle time scyc , the dumbbell
system will rotate 180 degrees every scyc divided by 2. This
rotation allows for the switching of the absorber between
the reduction and oxidation steps without having to switch
inlet streams. The rotation also allows the absorber to
Fig. 1. Schematic of receiver reactor with solar collector.
341
switch between being irradiated (during reduction) to not
being irradiated (during oxidation). The rotor in between
the two absorbers is insulated to ensure that the rotor is
not damaged by the high operating temperatures and no
heat transfer between the two absorber. The inlet ports
are also designed such that the reducing/oxidizing agent
enters the dumbbell absorber system from the top and bot-
tom. This top entrance ensures that there is no interference
of the solar irradiating the absorber during the reduction
from any inlet connections. Moreover, the dumbbell sys-
tem and the outer housing of the receiver reactor needs
to be manufactured such that the dumbbell system just fits
inside the housing to minimize any spillage of the inlet
streams. The reactor would also have to carefully assem-
bled to ensure that the inlet port of the dumbbell system
aligns with the inlet port of the housing. Note that due
to high temperature operation and the moving parts within
the reactor, the sealing of the inlet and outlet ports may not
be perfect and there can be spillage of gases (i.e., unre-
formed gases pass through the space in between the absor-
bers). However, as discussed previously, this reactor is
designed for use in hybrid solar-fossil fuel power genera-
tion rather than production of pure syngas. Thus, all the
products (whether reacted or not) are sent to a gas turbine
for power production. Therefore, the unreacted gases pass-
ing through the reactor is not necessarily a detriment for
the reactor. Since the two absorbers switch between the
two steps, they must be identical and the reduction and oxi-
dation time must be equal. Also note that during the
switching, the inlet gases would just flow through the reac-
tor to the outlet without undergoing any reforming. The
switching time is much smaller than the reduction/oxida-
tion time so therefore the amount of gases that do not pass
through the actual reforming site should be minimal.
As discussed previously, the absorber is a honeycomb
disk due to potential advantages in temperature distribu-
tion and fuel conversion. The absorber can be manufac-
tured from a number of different materials. The most
commonly used materials include Alumina, SiC, and Cor-
dierite. The selection of material is important as the absor-
ber material will also function as the support for the
oxygen carrier which is coated onto the channel surfaces.
For the base case results presented later, Alumina and
SiC are used for the absorber material. The length of the
absorber is chosen to be 50 mm based previous experimen-
tal studies for solar dry and steam reformers (Buck et al.,
1991; Skocypec et al., 1994). For this type of solar receiver
absorber, the absorber is often relatively short. The reason
is that the radiative flux decays quite rapidly in the axial
direction. This decay will be discussed in more detail when
the base case results are presented. The length is mainly
determined by the reaction kinetics. The absorber channel
width (d) is 4 mm based on previous experiments with hon-
eycomb absorbers (Levy et al., 1992). The length and chan-
nel size can have great effect on reactor performance.
Further sensitivity and optimization studies could be used
to select optimal channel design parameters.
342 E.J. Sheu, A.F. Ghoniem / Solar Energy 125 (2016) 339–359
(a)
Fig. 2. Conceptual schematic of receiver reactor: (a) simplified outer view of reactor, (b) simplified transparent view of reactor from front (left) and back
(right), (c) detailed schematic of reactor (side view).
During the reduction step, methane and a carrier gas
flows into the reactor. The carrier gas chosen here is CO2
to prevent coking that may occur during the methane
partial oxidation process. Note that steam can also be used
as the carrier gas in situations where CO2 is not readily
Fig. 3. Schematic of channel in computational model.
(b)
(c)
available. The CO2 also has the potential to further reform
the methane through the process of dry reforming; how-
ever, any dry reforming is neglected in this analysis due
to reasons that will be discussed later in Section 3.5. The
methane flow rate is chosen such that chemical energy of
the methane flowed into the reactor is 100 kW. The cycle
time is 6 min. This cycle time was chosen to achieve signif-
icant conversion (reduction) of the oxygen carrier during
the reduction step. The flow rate during the oxidation step
is also chosen such that the oxygen carrier is completely re-
oxidized (back to original state) during the time period for
oxidation (cycle time divided by 2). All parameters used for
the base case design of the reactor are summarized in
Table 3 (Section 4).
Now that the overall design of the reactor-receiver has
been presented. The computational model developed to
study this reactor will be discussed.
3. Computational model
For the computation model, the individual channel in
the solar absorber is modeled (Fig. 3). The model assumes
that one channel is representative of every other channel
(i.e., uniform temperature distribution across the face of
the absorber). The solid is relatively thin and
Biot number ¼ hds =k s  103
 E.J. Sheu, A.F. Ghoniem / Solar Energy 125 (2016) 339–359
where h is the heat transfer coefficient, ds is the solid thick-
ness, and k s is the thermal conductivity of the solid
(Table 3). Therefore the solid phase can be thought of as
a transient fin with temperature variation only along the
axial direction of the channel. The flow inside the channel
is laminar (Re < 100). Moreover, the ratio of channel
length to size (d  2ds ) is large (25); therefore the flow
is assumed to be fully developed for a large part of the
channel with an entrance region that is a relatively small
portion of the channel. The heat and mass transfer coeffi-
cient correlations do include entrance region effects. The
input solar flux is assumed to be already concentrated.
There is also no pressure drop taken into account as the
pressure drop calculated for laminar fully developed flow
is relatively small (<1 kPa) compared to the reactor operat-
ing pressure (20 bar).
The channels have a square cross section while the
absorber is a circular cross section (Fig. 2). Therefore, there
will be some non fully formed channels (i.e., not a square).
In the computational model, these channels are neglected.
As shown in Fig. 4, the reactor operation is modeled as
cyclic with two steps as follows: (1) Methane (along with a
carrier gas – CO2) is fed into the channel and metal reduc-
tion occurs, and (2) the input stream is switched from
methane to steam and metal oxidation occurs. During the
oxidation step, no solar energy is provided to the reactor.
The absorber switching time is not considered as that time
(on the order of seconds) is much smaller than the actual
reduction/oxidation time (on the order of minutes). The
model takes into account both the gas phase and the solid
phase (porous oxygen carrier layer and dense support) with
convective heat transfer and mass transfer between the
solid and gas phases (Fig. 4). Radiative transport from
the solar irradiation (when appropriate) and conductive
heat transfer are also taken into account in the solid phase.
The mass of the dense layer (ðds  doc Þqs ) is much
larger than that of the porous oxygen carrier layer
(ð1  s Þdoc qoc ) in order to minimize temperature fluctua-
tion and ensure thermal stability. Therefore, all heat
transfer properties for the solid are taken to be that of
the dense support. As mentioned previously, the absorber
material and is chosen to be alumina or SiC for the base
case results.
Fig. 4. Schematic of reactor operation model in channel during reduction
(top) and oxidation (bottom).
343
For the model initialization, the solid temperature is set
to the steady state solid temperature calculated assuming
no gas flow. To achieve a steady state, surface radiation
losses are taken into account at the front surface of the
channel. Without the gas flow, the solid temperature can
reach temperatures as high as 2000 K, which is what is
expected if the solid is merely being heated by the solar
radiation with only minimal surface radiation losses. For
every subsequent cycle, the initial condition for the appro-
priate variables (i.e., temperature) are set to the values
obtained at the end of the previous cycle. The model is con-
verged when the reformer has reached a cyclic steady state.
In this analysis the reformer is defined to have reached a
cyclic steady state when the temperature profile of the solid
is the same (<1 K difference) at the end of the cycle as it is
at the beginning of the cycle. Note that as the solid temper-
ature profile reaches a cyclic steady state, so does the gas
temperature profile.
The model is solved using COMSOL. The different
equations solved in the computational model will now be
discussed in more detail.
3.1. Species conservation
There are three different sets of species conservation
equations used in this model: one set for the species in
the gas phase, one set for the gas–solid interactions, and
a conservation equation for the oxygen carrier. The equa-
tions for the species conservation are as follows


@C i;g @ uC i;g
Gas : Ac þ Ac ¼ P c J gs;i ð1Þ
@t @x
Gas–solid interactions : 0 ¼ P c J gs;i þ P c Ri;s ð2Þ
@ð1  s ÞC oc
Oxygen carrier only : Aoc ¼ P c Roc ð3Þ
@t
where C i;g is the molar concentration of species i in the gas
flow (mol/m3), Ac is the cross sectional area of the channel
(m2), u is the velocity of the flow (m/s), P c is the perimeter
of the channel (m), Aoc is the cross sectional area of the oxy-
gen carrier layer (m2), s is the porosity of the solid, C oc is
the molar concentration of the oxygen carrier within the
porous layer (mol/m3), Ri;s is the surface reaction rate for
gaseous species i (mol/m2/s), Roc is the surface reaction rate
for the solid oxygen carrier (mol/m2/s). Both Ri;s and Roc
are dependent on the thickness of the porous layer (in addi-
tion to various kinetic parameters) and are discussed in
more detail later in Section 3.5. J gs;i is the molar flux of spe-
cies i between the solid and gas flow (mol/m2/s) and is
defined as
J gs;i ¼ hm ðC i;g  C i;s Þ ð4Þ
where hm is the mass transfer coefficient (m/s). The mass
transfer coefficient is calculated based on a simplified Sher-
wood number (Sh) correlation for laminar flow in catalytic
monoliths with a square cross section (Gundlapally and
Balakotaiah, 2011; West et al., 2003):
344 E.J. Sheu, A.F. Ghoniem / Solar Energy 125 (2016) 339–359

 13 total molar enthalpy (kJ/mol) of species i (not including the

d
Sh ¼ 3:089 þ 2:6099 Pem oxygen carrier) in either the gas (g) or solid (s) temperature,
L
^hj is the total molar enthalpy (kJ/mol) of the oxygen car-
where Pem is the Peclet number for mass transfer. This cor- rier, qr is the radiative flux in the solid (W/m2), and Qgs
relation includes the entry region effects and assumes unidi-
is the convective heat flux (W/m2) between the solid and
rectional within the channel (i.e., no flow in the y-
gas flow and is defined as
direction). This correlation also assumes constant mass flux
at the wall boundary (i.e., a slow reaction). Qgs ¼ hðT s  T g Þ ð7Þ
The velocity u is calculated from continuity:
where h is the heat transfer coefficient (W/m2/K). The heat
@ ðquÞ
¼0 transfer coefficient is calculated from the analogous Nusselt
@x number (Nu) correlation based on the previously discussed
where q is the molar density of the gas (mol/m3). While the Sherwood number correlation (Gundlapally and
gas temperature (and molar density) does change signifi- Balakotaiah, 2011; West et al., 2003):
cantly along the channel (i.e., @q @x
– 0), at a fixed point  13
d
within the channel, the temperature (and molar density) Nu ¼ 3:089 þ 2:6099 Peh
does not vary significantly with time throughout the cycle L
(Fig. 21). Therefore, the unsteady term in the continuity where Peh is the Peclet number for heat transfer. Again, this
equation is neglected. For the gas phase species conserva- correlation includes the entrance region effects and is for a
tion, axial diffusion effects are neglected due to the high square cross section and unidirectional flow.
Peclet number for mass transfer (Pem ¼ DLum  5e3). The solid and gas flow energy equations are coupled
For the gas–solid interaction equations, the accumula- through the convective heat flux. In addition, the energy
tion term is neglected as the gas volume in the oxygen car- released or consumed by the reactions is represented by
rier layer is much smaller than the gas volume in the gas the enthalpy (both chemical and thermal) that is being
phase and thus any amount of gas within the oxygen car- transferred between the solid and gas flow via the mass
rier layer is negligible compared to the gas phase flow. transfer. Moreover, within the solid, there is the extra term
The convection term is also neglected because the velocity for energy release/consumption due to the oxygen carrier
within the oxygen carrier layer is much smaller than the conversion. During the reduction step, there is solar irradi-
velocity in the gas flow due to surface drag. In other words, ation and thus within the solid, there is also the radiative
any gas species that are transferred from the gas flow to the flux due to the solar radiation present.
oxygen carrier layer is completely consumed and any pro- Note that for the solar radiation, the entire face of the
duct species generated by the reactions within the solid channel is considered to be irradiated. However, only the
are transferred to the gas flow. Moreover, all reactions solid is considered to transport radiation. The gas flow is
are assumed to occur in the solid as any gas phase reactions assumed to be a non-participating medium in radiation
would be much slower than the heterogeneous reactions transport due to the fact that the absorption coefficients
occurring in the solid. for typical gaseous species in the reactor are typically much
smaller than coefficients for the solid and thus can be
3.2. Energy conservation neglected (Petrasch et al., 2007). Furthermore, any radia-
tion that may be absorbed by the solid from the inner chan-
For energy conservation, there is one equation for the nel walls is assumed to be negligible as in a typical
solid and one equation for the gas flow. The two equations operation, the solar radiation would most likely penetrate
are as follows: the solid from the inner channel walls for only a small frac-

 tion of the channel near the inlet (side being irradiated).
@Eg @ uH g X
Gas : Ac þ Ac ¼ P c Qgs  P c J gs;i ^
hi;s ð5Þ Therefore, the error associated with assuming that all of
@t @z i the radiation is absorbed by the front solid surface should
@Es be minimal. There are also no additional radiative losses
Solid : As taken into account within the channel as the channel size
@t
  X is relatively small and thus the surface to surface radiation
@ @T s
¼ As k  P c Qgs þ P c J gs;i ^
hi;g between the upper and lower channel walls is assumed to
@z @z i be small (negligible temperature difference) and the channel
X @q wall is thin and thus the temperature variation in the y-
þ P c Rj ^
hj;s  As r ð6Þ
j
@z direction is very small (so no surface to surface radiation
losses within the channel wall). The details of the radiation
where E is the energy (J/m3) of either the gas (g) or solid transport modeling will be discussed next. Note that, as
(s), H is the enthalpy (J/m3) of the gas, T is the temperature mentioned previously, during oxidation there is no solar
(K), As is the cross sectional area of the solid (m2), ^hi is the radiation, so the radiative flux is not included.
 E.J. Sheu, A.F. Ghoniem / Solar Energy 125 (2016) 339–359 345

3.3. Radiation transport model where I c represents the collimated part of the radiative
intensity and the I d represents the diffuse part of the radia-
In this model, the solid is considered to be an absorbing, tive intensity.
emitting, and isotropically scattering material. The solid is The collimated part the radiative intensity can be calcu-
also assumed to have homogeneous and gray radiative lated as (Modest, 2013)
properties. In order to determine the radiative flux, the @I c
radiative intensity I must be determined. The one dimen- ¼ K ext I c ð12Þ
@z
sional transport equation based on the assumptions men-
tioned previously is as follows Substituting Eqs. (11) and (12) into Eq. (8) yields the fol-
Z 4p lowing equation for the diffuse part of the radiative
@I rs intensity
¼ ra I b ðT s Þ  K ext Ið^sÞ þ Ið^sÞdX0 ð8Þ
@z 4p 0 Z 4p
@I d rs
¼ ra I b ðT s Þ  K ext I d þ ðI d þ I c ÞdX0 ð13Þ
where I is the radiative intensity which is a function of @z 4p 0
direction vector ^s; ra is the absorption coefficient, rs is
To solve for these different radiative intensities a modi-
the scattering coefficient, K ext is the extinction coefficient
fied P1 approximation is used (Modest, 2013). The P1
(ra þ rs ), I b is the blackbody emission, and X is the angle
approximation is valid when the material is optically thick.
of the radiation.
Optical thickness can be calculated as (Modest, 2013)
The radiative properties (scattering, absorption, and
extinction coefficients) are determined from models using sL ¼ K ext L
geometrical optics. Geometrical optics are valid when
where sL is the optical thickness and L is the channel
(Petrasch et al., 2007)
length. For the materials used in the simulations, the opti-
pL cal thickness are approximately 15 and 10. Therefore all
a5
k optical thicknesses are greater than 1 and the material solid
can be considered to be optically thick.
where L is the channel (solid) length and k is the wave-
For solving using the P1 approximation, the incident
length of the radiation. For the typical wavelengths of solar
radiation function G will be used instead of the radiative
radiation and the base case parameters used herein
intensity I. The incident radiation function is defined as
pL
k
 105 . Thus since geometric optics are used the radiative Z 4p
properties are only dependent on the porosity of the solid. GðzÞ ¼ Ið^sÞdX ð14Þ
In this reformer, the solid properties are based on the dense 0
support layer, thus the radiative properties are taken for By using G the dependence on direction is removed which
materials that have very low porosity (<0.05%). makes for easier solving of equations. Similar to I; G can
The radiative flux (qr ) is the integration of radiative also be divided in collimated and diffuse parts yielding
intensity overall all angles in a specific direction
Z 4p G ¼ Gc þ Gd ð15Þ
qr ¼ Ið^sÞ^sdX ð9Þ Applying the P1 approximation, the diffuse radiative inten-
0
sity can be written as
For the the energy conservation equation, the gradient of 1
the radiative flux is needed and can be calculated as Id ¼ ðGd þ 3qd Þ ð16Þ
4p
Z 4p Z 4p
@qr @I Substituting Eq. (16) into Eq. (13) and integrating over all
¼ ^sdX ¼ 4pra I b ðT s Þ  K ext Ið^sÞdX
@z 0 @z 0 solid angles yields
Z 4p Z 4p 
rs @qd
þ Ið^sÞdX0 dX ð10Þ ¼ ra ð4pI b ðT s Þ  Gd Þ þ rs Gc ð17Þ
0 4p 0 @z
The radiative intensity within the solid has two distinct where qd is the radiative flux due to the diffuse radiative
parts: (1) the collimated portion which consists of the intensity.
remaining collimated beam from the solar radiation after To obtain an additional equation, substituting Eq. (16)
partial extinction, absorption and scattering and (2) the dif- into Eq. (13), integrating over all solid angles and multiply-
fuse portion which results from emission from boundaries ing by a specific direction vector yields
and within the medium and the scattered parts of the radi- 1 @Gd
ation from the collimated solar irradiation. For this model, qd ¼  ð18Þ
3K ext @z
it is assumed that the collimated solar radiation penetrates
directly into the solid without changing direction. Thus the Eqs. (17) and (18) are the governing equations for the mod-
radiative intensity can be rewritten as ified P1 approximation method (Modest, 2013).
Combining Eqs. (17) and (18) yields an equation for Gd
I ¼ Ic þ Id ð11Þ as
346 E.J. Sheu, A.F. Ghoniem / Solar Energy 125 (2016) 339–359
 
@ 1 @Gd This boundary condition is chosen because previous exper-
 ¼ ra 4pI b ðT s Þ  Gd þ rs Gc ð19Þ
@z 3K ext @z imental work has shown in these types of absorbers, the
solid temperature variation decreases towards the back half
Gc can be easily solved for from Eq. (12) and is equal to of the absorber (Muir et al., 1994).
Gc ¼ I o expðK ext zÞ ð20Þ Note that during the oxidation step (i.e., no radiation),
the front face boundary condition is still the same as the
After solving for Gd and Gc from Eqs. (19) and (20) explic- convection and surface radiation losses are again assumed
itly, the radiative flux term in Eq. (6) can be calculated to be minimal.
using Eq. (10) (integrated over all solid angles to use G For the radiative transfer equation, the radiation flux at
instead of I) as follows the front surface is set to the solar flux as discussed previ-
  ously and defined as
@qr @ 1 @G
¼  
@z @z 3K ext @z 1 @G
qr jz¼0 ¼  ¼ Io
3K ext @z z¼0
where G is the sum of Gd and Gc .
For the back end, Marshak’s boundary condition is used
3.4. Boundary conditions (Modest, 2013) and defined as
  
1 @Gd  1
For the species conservation, the boundary conditions  ¼ rT s jz¼L  Gd jz¼L
4

are simply based on the inlet flow rate of each of the 3K ext @z z¼L 4
species:
C i;g ðz ¼ 0Þ ¼ C i;in 3.5. Kinetics

For the gas flow energy equation, the boundary condition
is the inlet temperature of the gas flow.
T g ðz ¼ 0Þ ¼ T in
For the solid energy equation, an energy balance for the
front face (i.e., the side of the absorber being irradiated)
yields
qcond jz¼0 þ qr jz¼0 ¼ qconv jz¼0 þ qrad;s jz¼0 þ I o
where qcond is the conductive flux, qr is the radiation flux
transported within the solid, qconv is the convection heat
loss, qrad;s is the surface radiation loss, and I o is the input
solar flux. The solar absorbers used in these types of solar
receivers are often coated such that they completely absorb
the solar radiation (Ávila Marı́n, 2011). Thus, the surface
radiation loss is assumed to be minimal. Moreover, the
convective heat loss is also assumed to be minimal as the
solar receiver is usually constructed such that there is insu-
lation to minimize the convection loss. Finally, at the irra-
diated surface the radiation flux dominates over the
conduction loss. Therefore, the radiation flux at the surface
is assumed to be equal to the input solar flux. This assump-
tion also leads to the following boundary condition for the
temperature gradient

@T s 
¼0
@z z¼0
where essentially the front surface is non-conducting.
For the other side of the solid (i.e., the exit), the bound-
ary condition is such that the surface is adiabatic or
mathematically,
 a
@T s 
¼0
@z z¼L
To model the chemical reaction kinetics, kinetics param-
eters from two different studies were used. The different
kinetic parameters for both the reduction and oxidation
step are summarized in Table 1. How these parameters
are used in the rate expressions as well as the experimental
conditions used to obtain these parameters will be dis-
cussed next.
3.5.1. Reduction
As discussed previously, the reduction reaction for the
reformer studied here is
CH4 þ Fe3 O4 ! 3FeO þ CO þ 2H2 DH o ¼ 266:60 kJ=mol
The kinetics parameters are taken from (Moghtaderi and
Song, 2010). This kinetics study was done for the reduction
of hematite to wustite with methane (Fe2 O3 ! FeO). The
reduction of iron oxide occurs in steps – hematite
(Fe2O3) ? magnetite (Fe3O4) ? wustite (FeO) ? iron
(Fe) (Adanez et al., 2012). The first reduction stage
(Fe2O3 ? Fe3O4) is what is most often used in chemical
looping combustion and is a comparatively fast process
(Adanez et al., 2012). Therefore, despite the study not
being done for the exact same reaction utilized herein,
Table 1
Kinetic parameters used in computation model
(Moghtaderi and Song, 2010; Stehle et al., 2015).
Kinetic parameter Value
k 0;red 4e2 [mol0.2 m0.6 s1]
Ea;red 25 [kJ/mol]
0.89
k 0;oxd 4e3 [mol0.5 m0.5 s1]
Ea;oxd 47.3 [kJ/mol]
 E.J. Sheu, A.F. Ghoniem / Solar Energy 125 (2016) 339–359
the kinetics parameters should still be suitable since the
step that is actually being used can be seen as the rate-
limiting step. Furthermore, it is assumed that only FeO is
formed during reduction and is not further reduced to Fe
since there is always Fe3O4 available for reduction (oxygen
carrier not fully reduced during reactor operation) and
therefore, the further reduction of FeO to Fe should be
minimal due to reduction stages of the oxygen carrier.
The kinetics from (Moghtaderi and Song, 2010) are one-
step extrinsic kinetics. The oxygen carrier is prepared by
direct mixing of Fe2O3 and alumina powders. A paste
was then created from this mixture before being dried
and calcined. The calcined paste was then pulverized in a
ball mill with particle sizes in the range of 90–106 lm
(Moghtaderi and Song, 2010). The oxygen carrier has a
58% wt. active metal oxide content. The kinetic data was
obtained using thermogravimetric analysis in the tempera-
ture range of 800–950 °C at atmospheric pressure. Methane
is used as the reducing agent with Argon as the carrier gas
(Moghtaderi and Song, 2010).
The kinetic parameters derived from this study are
based on the shrinking core model for spherical grain
geometry. Therefore, the conversion rate is written as
(Moghtaderi and Song, 2010)
dX 2
¼ 3ð1  X Þ3 k red C 0:2
g ð21Þ
dt
where X is the conversion of Fe3O4 to FeO (X ¼ 0 at start
of reduction), C g is the concentration of reducing gas
(methane), and k red is the Arrhenius rate constant defined
as
 
Ea;red
k red ¼ k 0;red exp ð22Þ
RT
where R is the universal gas constant and k 0;red and Ea;red
are pre-exponential factor and activation energy, respec-
tively, determined from experiments (Table 1).
Since these kinetics are based on spherical particles and
in the reformer the oxygen carrier is basically used with a
plate-like geometry (porous layer atop a support layer),
special attention must be paid as to how the geometry
can affect the reaction rate. The two main ways that the
geometry can affect the reaction rate are external mass
transfer and internal diffusion. The external mass transfer
is already characterized by Eq. (2). The internal diffusion,
however, is inherently part of the kinetics as the kinetics
are extrinsic. Moreover, the experiments were done assum-
ing minimal internal diffusion effects. Therefore, in order to
apply these kinetics to the solar steam redox reformer, the
thickness of the porous layer (Table 3) must be chosen
carefully to ensure that the internal diffusion is indeed min-
imal. In order to ensure that the internal diffusion is similar
between the spherical geometry utilized in the experiment
and the plate like geometry used in the reformer, the con-
version times for internal diffusion should be matched
(Zhao et al., 2013). In order to match the two conversion
times, the thickness of the oxygen carrier layer needs to
347
be on the order of 2ppffiffi3 where d p is the particle size (Zhao
d
et al., 2013). For the particle size used in the experiment,
the oxygen carrier layer thickness should be between 26
and 31 lm. The chosen oxygen carrier layer thickness
(30 lm) falls within this range. In addition to porosity of
the layer is chosen to be the same as the porosity used in
the kinetics experiment (Moghtaderi and Song, 2010).
As this study was done at atmospheric pressure, there is
no pressure dependence for the conversion rate. Based on
chemical looping combustion studies the pressure depen-
dence can be written as (Abad et al., 2007)
k0
k 0;p ¼ ð23Þ
Pa
where k 0;p is the pre-exponential factor at pressure P ; k 0 is
the pre-exponential factor at atmospheric pressure, and a
is the pressure coefficient determined for experiment. The
value of a used here in (Table 1) is taken from the study
done with CO/H2 as the reducing agent as there was no
data found for methane (Abad et al., 2007).
Including this pressure dependence yields the following
expression for the conversion rate:
 a
dX P 2
¼3 ð1  X Þ3 k red C 0:2
g ð24Þ
dt Po
where P is the pressure of the reactor and P o is the atmo-
spheric pressure.
To give an idea of what times are needed for significant
oxygen carrier conversion, the oxygen carrier conversion
versus time is shown in Fig. 5. Note that the plot shows
the conversion for typical reformer operating conditions
(i.e., pressurized condition).
As discussed previously, the internal diffusion is mini-
mal. Therefore, the conversion rate shown in Eq. (24) can
be adapted for this study using parameters pertaining to
the oxygen carrier and the stoichiometric coefficients for
species i as follows
mi dX
Ri;s ¼ q voc doc ð25Þ
moc oc dt
where mi is the stoichiometric coefficient of species i; mo c is
the stoichiometric coefficient of the oxygen carrier, voc is
the volume fraction of the oxygen carrier, and doc is the
thickness of the oxygen carrier layer.
As mentioned previously, CO2 is used as a carrier gas
during the reactor operation. CO2 has the potential to react
at the surface with the methane to produce more syngas
through dry reforming. Experimental work with dry
reforming and FeO as the catalyst has been done before
(Gokon et al., 2002). This study found that the presence
of Fe3O4 had no effect on the dry reforming reaction sug-
gesting that the magnetite stage (the fully oxidized stage
in this reactor) is not a catalyst for the dry reforming reac-
tion (Gokon et al., 2002). However, there is still the poten-
tial for the FeO that is produced during the reduction step
to catalyze the dry reforming reaction. From the study
done in (Gokon et al., 2002), it was concluded that the
348 E.J. Sheu, A.F. Ghoniem / Solar Energy 125 (2016) 339–359
0.8
T = 1000 K
0.7
T = 1100 K
0.6
T = 1200 K
T = 1300 K
Conversion X (−)
0.5
0.4
0.3
0.2
0.1
0 where in this case, C g is the concentration of steam and k oxd
0 1 2 3 4 5 6 7
Time (min)
Fig. 5. Conversion of oxygen carrier versus time for reduction step (for
typical reformer operating conditions).
mechanism for the dry reforming reaction was simply a
redox cycle with the methane reducing the FeO to Fe and
the CO2 present oxidizing the Fe back to FeO. Since in
our reactor, the metal oxide is never fully reduced, there
will always be Fe3O4 available to be reduced and therefore
since as discussed previously the reduction of iron oxide is
in stages, the CH4 reduction of Fe3O4 would dominate over
the FeO reduction reaction. Therefore, the first step in the
dry reforming reaction is likely very slow as compared to
the main reaction of the reduction step and thus, overall
the dry reforming reaction will be much slower than the
main reduction reaction. Because of this comparatively
slower rate, the dry reforming reaction is not accounted
for in the reduction step chemistry.
3.5.2. Oxidation
The oxidation reaction for this reformer is
3FeO þ H2 O ! Fe3 O4 þ H2 DH ¼ 60:44 kJ=mol
o dt
For the oxidation kinetics, the parameters from (Stehle
et al., 2015) are used. The kinetics study was done for the
oxidation of an iron rod to magnetite with steam or CO2.
During the oxidation of pure iron with steam, wustite
(FeO) is an intermediate formed during oxidation but then
is readily oxidized to the final magnetite stage at the end of
oxidation (Stehle et al., 2011). Therefore, even though the
current reformer oxidizes wustite to magnetite rather than
pure iron, these kinetics parameters can be seen as a con-
servative estimate and still valid for use. However, it should
be noted that this kinetic study is done with an iron rod
rather than a porous oxygen carrier layer on a support
which is what is modeled herein. This difference can be
important in terms of reaction rates. There have been pre-
vious kinetic studies for doped ferrites or iron oxide based
porous structures (Mehdizadeh et al., 2012); however in
order to match the reactor design, which uses pure iron
oxide as the oxygen carrier, the kinetics parameters from
(Stehle et al., 2011) will be used. Note that the model can
always be improved with more accurate kinetics.
As mentioned previously the kinetic study is done with
an iron rod. The experiments were done in a temperature
range of 973–1473 K which matches well with the typical
operating temperatures of the solar reformer. Steam was
fed into the iron system along with an inert gas (Argon
and Helium). The kinetics parameters obtained are based
on the Cabrera-Mott model with the chemisorption step
as rate limiting. The hydrogen production rate can then
be expressed as
dH2
¼ k oxd C g0:5 ð26Þ
dt
8
is defined similarly to the reduction case as
 
Ea;oxd
k oxd ¼ k 0;oxd exp ð27Þ
RT
where again k 0;red and Ea;red are the pre-exponential factor
and activation energy, respectively, determined from exper-
iments (Table 1).
In this reaction rate, there is no dependence on availabil-
ity of oxygen carrier. In the reformer modeled herein, the
oxidation reaction rate should have a dependence on oxy-
gen carrier available as when oxidation is complete, the
reaction should no longer continue. To include this depen-
dence the oxygen carrier conversion is added to the reac-
tion rate with an order of one (reason for this
dependence is explained later) which yields the following
expression for the hydrogen production rate:
dH2
¼ Xk oxd C 0:5
g ð28Þ
dt
This hydrogen production rate can then be converted to an
oxygen carrier conversion rate as follows:
dX moc
¼ Xk oxd C 0:5
g ð29Þ
qoc voc doc
The first order dependence for the conversion on the reac-
tion rate is chosen because the conversion of the oxygen
carrier with time calculated from this expression (Fig. 6)
is of the same order of magnitude of other experiments
done with steam oxidation in the literature (Stamatiou
et al., 2010).
From the modified Hydrogen production rate, the gen-
eral reaction rate for species i to be used in the species con-
servation modeling can be expressed as
Ri;s ¼ mi Xk oxd C 0:5 ð30Þ
g
3.6. Numerical validation
As there is no experimental data with this exact type of
solar reformer, the model is validated as follows: first, the
heat transfer modeling is validated by comparing model
results with literature results for a solar receiver used to
 E.J. Sheu, A.F. Ghoniem / Solar Energy 125 (2016) 339–359
1 to the literature results. It should be noted that for the lit-
0.9
T = 1000 K
T = 1100 K
0.8 T = 1200 K
T = 1300 K
0.7
Conversion X (−)
0.6
0.5
0.4
0.3
0.2
0.1
0 reformer via a drop wise application of RuCl3 and ethanol
0 1 2 3 4 5 6 7
Time (min)
Fig. 6. Conversion of oxygen carrier versus time using modified rate
expression for oxidation (for typical reformer operating conditions).
heat up air (Wu et al., 2011) then second, the species con-
servation modeling is validated by comparing to an exper-
imental study of a solar dry reformer at isothermal
conditions (Gokon et al., 2009). For both steps of the val-
idation, model parameters are set to those used in the liter-
ature studies. Thus, the parameters do not match with what
are used in the base case results that will be presented later.
However, this validation does illustrate whether the model
equations that are used are valid and whether they are
being numerically solved correctly. When presenting the
base case results, the reasonableness of those specific results
will be discussed.
For the heat transfer modeling validation, the model
results are compared to the study done by Wu et al.
(2011) (Fig. 7). Since this part is just for the heat transfer
modeling, the species conservation modeling is not taken
into account. The Wu et al. study is done for turbulent
flow. Thus, to validate the model with the literature results,
the fluid temperature is taken as an input and the solid tem-
perature is compared. Model parameters such as absorber
length and heat transfer coefficient are taken from (Wu
et al., 2011). The results are compared for several different
inlet velocities. For completeness, the radiative flux calcu-
lated is also shown in Fig. 8. The radiation flux monoton-
ically decreases along the channel and decays very quickly.
For the most part, the model results match reasonably well
with the literature results (Fig. 7). There are some discrep-
ancies at the front face of the absorber. This discrepancy
can be due to the channel width/solid thicknesses values
used. As mentioned previously, the literature study is done
for a porous media; therefore, the parameters for channel
size used in the model are estimated from the pore size
given for the literature study.
The difference in these parameters can affect not only the
front surface temperature (due to differing solid surface
area) but also the other heat transfer processes (i.e., con-
vection). Overall, the model results match reasonably well
349
erature study, the velocities at which the air is sent into the
absorber is much faster than any typical operation for the
solar reformer. This very high velocity leads to the rela-
tively low temperatures as well as the very fast equilibra-
tion between the solid and gas temperature. Therefore,
the temperature results are not necessarily representative
of what the reformer temperature results will be.
For the species conservation modeling, as mentioned
previously, the model results are compared to an
experimental study for dry reforming of methane in a
Ni–Cr–Al alloy foam absorber (Gokon et al., 2009). The
absorber is coated with c-Alumina support particles by
the washcoat method. Then Ruthenium is loaded on the
8
solution. The Ru loading is such that it is 30 wt% of the
mass of the support. The absorber is placed in a tubular
quartz reactor which is within an electric furnace. The reac-
tant gases are sent in from one end of the reactor through
the absorber and then the methane conversion is measured
at the other end of the reactor. The methane conversion is
measured at four different temperatures: 600 °C, 650 °C,
700 °C, and 750 °C. The ratio of Methane to Carbon
Dioxide is set to 1 and Argon is used as a carrier gas.
The comparison of the methane conversion measured
experimentally and the methane conversion calculated
from the model is shown in Fig. 9. Note that channel
dimensions are estimated from pore properties in experi-
ment. Also note that for this comparison, since the exper-
imental study is for dry reforming and not redox
reforming, the kinetics of the computational model are
changed to match those of the experimental study. For
the experimental study, the kinetics are based on the Lang-
muir–Hinshelwood model with the reaction rate dependent
on partial pressures and various parameters determined
experimentally including rate constant and adsorption
equilibrium constants (Gokon et al., 2009). The experimen-
tal study is also done at isothermal conditions so the heat
transfer modeling is not taken into account during this part
of the validation.
From Fig. 9 it can be seen that overall the methane con-
version calculated from the model is consistent with the
experimental results from literature. There is a larger dis-
crepancy at the higher temperature likely because the kinet-
ics parameters best matched experimental results in the
600–700 °C range (Gokon et al., 2009), and thus a larger
discrepancy at the higher temperature would be expected.
Thus, since the results match reasonably well, the species
conservation model can be considered valid.
Overall, the literature studies used from comparison are
not necessarily representative of the solar steam redox
reformer operation; however, they do allow for validation
of the model equations themselves. With the differing
parameters used in the base case results, the reasonableness
of those results will also be discussed later.
Now that the model have been validated, the base case
simulation results and their validity will be discussed.
350 E.J. Sheu, A.F. Ghoniem / Solar Energy 125 (2016) 339–359

Inlet Velocity = 2.16m/s Inlet Velocity = 1.73m/s

600 600

550 550

Temperature (K)

Temperature (K)
500 500

450 450

400 400

350 350

300 300
0 0.01 0.02 0.03 0.04 0.05 0 0.01 0.02 0.03 0.04 0.05
Position (m) Position (m)
Inlet Velocity = 1.30m/s Inlet Velocity = 1.08m/s
700 700
Temperature (K)

Temperature (K)
600 600

500 500
T - Lit
f
T - Lit
s
400 400 T - Model
s

300 300
0 0.01 0.02 0.03 0.04 0.05 0 0.01 0.02 0.03 0.04 0.05
Position (m) Position (m)

Fig. 7. Comparison between model and literature results for validation of energy conservation numerics (Wu et al., 2011).

600 24

22
500 Literature
20 Model
Methane Conversion (%)
Energy Flux (kW/m 2 )

400 18

16
300
14

200 12

10
100
8

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045 0.05 6
600 650 700 750
Position (m)
Temperature ( oC)
Fig. 8. Radiative flux along channel for heat transfer modeling validation.
Fig. 9. Comparison between model and literature results for validation of
species conservation numerics (Gokon et al., 2009).
4. Base case results
taken for low porosity alumina/SiC solids or honeycomb
For the base case, both an alumina absorber and SiC (Skocypec et al., 1994; Pitz-Paal et al., 1997). Note that
absorber are simulated. The alumina absorber is simulated as discussed previously, the absorber front face is assumed
to compare model results to previous experimental work in to be coated such that the emissivity of the absorber is very
order to examine whether the model results agree with small which means the surface radiation losses are minimal.
trends observed previously. The SiC absorber is simulated The reactor design and operating parameters used for
to determine if a material with a higher thermal conductiv- the base case results are shown in Table 3. The concen-
ity is beneficial to overall reactor performance. The proper- trated solar irradiation value (400 kW/m2) was chosen
ties of the oxygen carrier and absorber/support materials based on values obtained for an actual reformer integrated
are summarized in Table 2. The optical properties are with a parabolic dish (Buck et al., 1991). As discussed
 E.J. Sheu, A.F. Ghoniem / Solar Energy 125 (2016) 339–359 351

Table 2 0.18
Oxygen carrier and support material properties.
Parameter Alumina SiC 0.16
u @ 0.1*L
Conductivity of solid (k s ) 30 [W/m/K] 100 [W/m/K] u @ 0.5*L
Density of solid (qs ) 3900 [kg/m3] 3200 [kg/m3] 0.14 u @ outlet

Porosity of oxygen carrier layer (s ) 0.32 0.32

Velocity (m/s)
Volume fraction of oxygen carrier (voc ) 0.45 0.45 0.12
Absorption coefficient (ra ) 140 [m1] 50 [m1]
Scattering coefficient (rs ) 160 [m1] 151 [m1]
0.1
Reduction (With Solar) Oxidation (No Solar)
0.08
Table 3
Design and operating parameters used for base case results.
0.06
Parameter Value
Absorber diameter (D) 40 [cm] 0.04
Channel size (d) 4 [mm] 0 50 100 150 200 250 300 350
Channel length (L) 50 [mm] Time (s)
Thickness of solid (ds ) 1 [mm]
Thickness of oxygen carrier layer (doc ) 30 [lm] Fig. 10. Gas velocity profile throughout cycle at different points along the
Cycle time (scyc ) 6 [min] channel for Alumina absorber (reduction: t = 0–180 s, oxidation: t = 180–
Volume fraction of fuel at inlet 0.5 360 s).
Fuel flow velocity (ured ) 0.1 [m/s]
Steam flow velocity (uoxd ) 0.04 [m/s] where gCH 4 is the cycle average methane conversion, m_ CH 4 is
Pressure (P) 20 [bar]
Inlet gas temperature (T in ) 800 [K]
methane flow rate at the inlet and outlet of the channel,
Solar irradiation (I o ) 400 [kW/m2] and the integration over time is for only the reduction step.
The oxygen carrier conversion is defined as
previously the flow rate during reduction is determined C oc;FeO
X ¼ ð32Þ
such that the chemical energy of the inlet fuel flow is C oc;FeO þ C oc;Fe3 O4
100 kW. The fuel flow rate is such that the total solar input where X is the oxygen carrier conversion, C oc;FeO and
is approximately 10% of the total fuel and solar input. The C oc;Fe3 O4 are the molar concentrations of the two states of
flow rate during oxidation is chosen such that all the oxy- the oxygen carrier (wustite and magnetite). X is one when
gen carrier can be fully oxidized. The cycle time is chosen the oxygen carrier is fully reduced and is zero when it is
such that there is a base case oxygen carrier conversion fully oxidized.
of approximately 30% (Fig. 17). Note that the cycle time The solar utilization efficiency is defined as
in essence determines the oxygen carrier conversion, and
for this base case, the oxygen carrier conversion is on the DH p jT p
gsu ¼ ð33Þ
lower end since that is not the objective of this reactor. Fur- DH r jT r þ Qsolar
thermore, very high or complete oxygen carrier can lead to
material degradation over time. The inlet gas temperature
(800 K) is chosen based on operation of reformer within 1500

a hybrid solar-fossil fuel power cycle.

T solid @ inlet
The reformer is simulated using the base case parame-
1450 T @ 0.5*L
ters and the results are shown in Figs. 10–23. The results solid
T solid @ outlet
shown include the velocity profile throughout the redox
Temperature (K)

cycle, the reactor temperature profile throughout the redox 1400

cycle at different points along the channel, the methane
conversion, and the oxygen carrier conversion along the
channel throughout the reduction step. In addition the 1350
overall reactor performance is evaluated based on cycle
average methane conversion, a solar utilization efficiency,
1300
a chemical efficiency, oxygen carrier conversion, and max-
imum temperature variation within the reactor solid. The Reduction (With Solar) Oxidation (No Solar)
overall reactor performance results are summarized at the 1250
end of the discussion in Table 4. 0 50 100 150 200 250 300 350
The cycle average methane conversion is defined as Time (s)
R
m_ CH 4 ;out dt Fig. 11. Reactor temperature profile throughout cycle at different points
gCH 4 ¼ 1  Rred ð31Þ along the channel for Alumina absorber (reduction: t = 0–180 s, oxida-
red
m_ CH 4 ;in dt tion: t = 180–360 s).
352 E.J. Sheu, A.F. Ghoniem / Solar Energy 125 (2016) 339–359

t = 0s t = 60s
400 400

Energy Flux (kW/m 2 )

Energy Flux (kW/m 2 )
300
200
200
0
100

-200 0
0 0.01 0.02 0.03 0.04 0.05 0 0.01 0.02 0.03 0.04 0.05
Position (m) Position (m)
t = 120s t = 180s
400 400
Energy Flux (kW/m 2 )

Energy Flux (kW/m 2 )

300 300

200 200

100 100

0 0
0 0.01 0.02 0.03 0.04 0.05 0 0.01 0.02 0.03 0.04 0.05
Position (m) Position (m)
t = 240s t = 300s
10
Energy Flux (kW/m 2 )

Energy Flux (kW/m 2 )

0
0

-10 -20
-20
-40 Radiation Flux
-30
Conduction Flux

-40 -60
0 0.01 0.02 0.03 0.04 0.05 0 0.01 0.02 0.03 0.04 0.05
Position (m) Position (m)
@G
Fig. 12. Radiation (qr ¼  K1ext @z
) and conduction flux (qcond ¼ k s @T
@z
) along channel throughout cycle for Alumina absorber.

1330 1550

1500
1320 300 kW/m 2
2
1450 400 kW/m
2
500 kW/m
Temperature (K)

Temperature (K)

1310
1400

1300 1350

1300
1290
1250
1280
1200

1270 1150
0 20 40 60 80 100 120 140 160 180 0 20 40 60 80 100 120 140 160 180
Time (s) Time (s)

Fig. 13. Reactor gas outlet temperature throughout reduction step (with Fig. 14. Average reactor temperature throughout the reduction step for
solar radiation) for Alumina absorber. different concentrated solar fluxes.

where DH p jT p and DH r jT r is the enthalpy of the reformer actually used within the reactor whether through heating
or reforming.
products and reactants at product temperature T p and
The chemical efficiency is defined as
reactant temperature T r , respectively, and Qsolar is the
amount of solar energy entering reactor. The solar utiliza- DH op
gchem ¼ ð34Þ
tion efficiency represents how much of the solar energy is DH or þ Qsolar
 E.J. Sheu, A.F. Ghoniem / Solar Energy 125 (2016) 339–359 353

t = 0s t = 60s
1400 1600

Temperature (K)
Temperature (K)
1400
1200
1200
1000
1000

800 800
0 0.01 0.02 0.03 0.04 0.05 0 0.01 0.02 0.03 0.04 0.05
Position (m) Position (m)

t = 120s t = 180s
1600 1600

Temperature (K)
Temperature (K)

1400 1400

1200 1200

1000 1000

800 800
0 0.01 0.02 0.03 0.04 0.05 0 0.01 0.02 0.03 0.04 0.05
Position (m) Position (m)

t = 240s t = 300s
1400 1400
Temperature (K)
Temperature (K)

1200 1200

T gas
1000 1000 T
solid

800 800
0 0.01 0.02 0.03 0.04 0.05 0 0.01 0.02 0.03 0.04 0.05
Position (m) Position (m)

Fig. 15. Comparison of solid and gas temperature along the channel for different times throughout cycle for Alumina absorber (reduction: t = 0–180 s,
oxidation: t = 180–360 s).

58 0.45
t = 0s
0.4 t = 60s
57 t = 120s
Oxygen Carrier Conversion (-)

t = 180s
0.35
Methane Conversion (%)

56
0.3
55
0.25
54
0.2
53
0.15

52 0.1

51 0.05

0
50 0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045 0.05
0 20 40 60 80 100 120 140 160 180
Time (s) Position (m)

Fig. 16. Instantaneous methane conversion during reduction step for Fig. 17. Oxygen carrier conversion along channel during reduction step
Alumina absorber. for Alumina absorber.

This chemical efficiency can be thought of as a cold gas effi-

where DH op and DH or is the enthalpy of the reformer prod- ciency and shows how much of the solar energy is used for
ucts and reactants at standard temperature, respectively. just reforming.
354 E.J. Sheu, A.F. Ghoniem / Solar Energy 125 (2016) 339–359

0.18 state operation. Note that there is also additional startup

time where the temperatures are changing as well before
0.16 u @ 0.1*L the cyclic steady state is reached. How the modeled is ini-
u @ 0.5*L
u @ outlet tialized and the method for reaching a cyclic steady state
0.14 is discussed previously in Section 3. Fig. 11 also shows that
the inlet of the channel experiences a larger temperature
Velocity (m/s)

0.12 variation with time than the outlet of the channel. During
reduction, the radiation/conductive heat transfer (which
0.1 Reduction (With Solar) Oxidation (No Solar) raises the temperature) dominates over the chemical reac-
tion energy transfer (which lowers the temperature due to
0.08 the endothermic nature of the reaction) near the inlet of
the channel. Moving along the channel, the chemical reac-
0.06
tion energy transfer (the thermal energy required for the
endothermic reduction reaction) starts to dominate. Also
0.04
0 50 100 150 200 250 300 350 note that the spatial temperature variation decreases along
Time (s) the channel (i.e., temperature variation within first half of
channel is much larger than temperature variation within
Fig. 18. Gas velocity profile throughout cycle at different points along the
second half). This matches what has been observed in solar
channel for SiC absorber (reduction: t = 0–180 s, oxidation: t = 180–
360 s). reformer experimental studies where most of the tempera-
ture variation occurred in the front half of the absorber
(Buck et al., 1991; Skocypec et al., 1994). The decrease in
1420 variation also shows that the adiabatic boundary condition
T solid @ inlet at the back surface is reasonable. During oxidation, there is
1400 T solid @ 0.5*L
no longer any solar irradiation. The reactor is mainly
T @ outlet
1380
solid cooled by convection because the oxidation reaction is only
slightly exothermic. Moreover, the front face temperature
Temperature (K)

1360 also decreases substantially due to the absence of solar irra-

diation on the surface.
1340
To show the relative magnitudes of the conductive and
1320 radiative fluxes, the profile of the two fluxes along the
channel is shown in Fig. 12 at various times throughout
1300 the cycle. There are two transient states when the reactor
is switched between the reduction and oxidation steps
1280
and then a steady state profile is reached within each step.
Reduction (With Solar) Oxidation (No Solar)
1260
During reduction, the radiation flux (qr ¼  K1ext @G @z
) domi-
0 50 100 150 200 250 300 350
nates over the conduction flux (qcond ¼ k s @T @z
) closer to
Time (s)
the inlet. Further downstream, the conduction flux
Fig. 19. Reactor temperature profile throughout cycle at different points becomes more dominant. This result suggests that the
along the channel for SiC absorber (reduction: t = 0–180 s, oxidation: assumption of a non-conducting front face surface (or min-
t = 180–360 s).
imally conducting surface) is valid. During oxidation, the
radiation flux is minimal due to the absence of the solar
The Alumina absorber results will now be discussed in radiation source. Moreover, the conduction flux is also
more detail followed by the discussion of the SiC absorber smaller due to less temperature variation.
results. It should be noted that during reduction, the ‘‘radiative
source term” (i.e., @q
@z
r
) decays rapidly and becomes zero less
4.1. Alumina absorber than halfway along the channel. Thus making the absorber
(channel) length longer only improves the conversion due
First, the gas velocity at different points along the chan- to the higher residence times. During oxidation, the ‘‘radia-
nel throughout the cycle is shown in Fig. 10. As can be seen tive source term” is essentially zero since the radiative flux
from Fig. 10, the velocity increases along the channel due is relatively constant along the channel.
to the increasing temperature. The velocity during the oxi- As mentioned previously, the temperature variation
dation is lower due to the different inlet velocities. throughout the reactor is quite large. From previous exper-
Next, the temperature profiles at different points along iments with a dry reformer using an Alumina absorber with
the channel throughout the cycle are shown in Fig. 11. a parabolic dish, the temperature variation along the
The temperature at the end of the cycle is the same as the absorber was measured to be between 100–200 degrees
temperature at the beginning, confirming a cyclic steady for solar fluxes between 300 and 500 kW/m2 (Skocypec
 E.J. Sheu, A.F. Ghoniem / Solar Energy 125 (2016) 339–359 355

t = 0s t = 60s
400 400

Energy Flux (kW/m 2 )

Energy Flux (kW/m2 )
300
200
200
0
100

-200 0
0 0.01 0.02 0.03 0.04 0.05 0 0.01 0.02 0.03 0.04 0.05
Position (m) Position (m)

t = 120s t = 180s
400 400
Energy Flux (kW/m 2 )

Energy Flux (kW/m 2 )

300 300

200 200

100 100

0 0
0 0.01 0.02 0.03 0.04 0.05 0 0.01 0.02 0.03 0.04 0.05
Position (m) Position (m)

t = 240s t = 300s
10 10
Energy Flux (kW/m 2 )
Energy Flux (kW/m 2)

Radiation Flux
5 5 Conduction Flux

0 0

-5 -5

-10 -10
0 0.01 0.02 0.03 0.04 0.05 0 0.01 0.02 0.03 0.04 0.05
Position (m) Position (m)
@G
Fig. 20. Radiation (qr ¼  K1ext @z
) and conduction flux (qcond ¼ k s @T
@z
) along channel throughout cycle for SiC absorber.

et al., 1994; Muir et al., 1994). The concentrated solar flux operation. This case will be discussed later when discussing
used in the base case (400 kW/m2) falls within the range the SiC absorber.
used in the experimental study, and the temperature profile A comparison of solid and gas temperature along the
in Fig. 11 shows that the maximum temperature variation channel length throughout the cycle is also shown in
within the solid during the reduction step is around 150 Fig. 15. At the channel outlet, the gas temperature is essen-
degrees which falls within this range. In addition, for the tially equal to the solid temperature. Fig. 15 also shows
same range of solar fluxes the outlet reactor temperature that during reduction the maximum solid temperature is
is between 800 and 1100 °C (Skocypec et al., 1994; Muir at the front face (where the solar radiation is) and during
et al., 1994) which also matches well with the results oxidation the maximum solid temperature is within the
(Fig. 13). channel.
As the amount of concentrated solar flux can greatly Moving onto conversion, the instantaneous methane
affect the temperature results, the average reactor tempera- conversion during the entire reduction step is shown in
ture calculated from the model for the range of solar fluxes Fig. 16. Similar to the cycle average methane conversion,
used in previous experimental studies is shown in Fig. 14. the instantaneous methane conversion is defined as
As expected, as the amount of solar flux increases, the reac- R
m_ CH 4 ;out dt
tor temperature increases. Again these reactor tempera- gCH 4 ¼ 1  R1s ð35Þ
tures are of the same order of magnitude as previous m_
1s CH 4 ;in
dt
experimental results (Skocypec et al., 1994; Muir et al., where gCH 4 is the instantaneous methane conversion, m_ CH 4
1994). is methane flow rate at the inlet and outlet of the channel.
Since the temperature variation along the channel solid Essentially the instantaneous methane conversion is the
is quite high, absorber material degradation during solar conversion corresponding to one second of time through-
reforming tests has been observed (Buck et al., 1991; out the reduction step rather than a cycle average.
Muir et al., 1994). Therefore, a higher thermal conductivity The instantaneous methane conversion decreases during
absorber material might be beneficial for long term reactor the reduction step as the reaction rate decreases due to the
356 E.J. Sheu, A.F. Ghoniem / Solar Energy 125 (2016) 339–359

t = 0s t = 60s
1300 1400

Temperature (K)

Temperature (K)
1200
1200
1100

1000
1000
900

800 800
0 0.01 0.02 0.03 0.04 0.05 0 0.01 0.02 0.03 0.04 0.05
Position (m) Position (m)
t = 120s t = 180s
1400 1600
Temperature (K)

Temperature (K)
1400
1200
1200
1000
1000

800 800
0 0.01 0.02 0.03 0.04 0.05 0 0.01 0.02 0.03 0.04 0.05
Position (m) Position (m)

t = 240s t = 300s
1400 1400
Temperature (K)

Temperature (K)

1200 1200

T
gas
1000 1000 T solid

800 800
0 0.01 0.02 0.03 0.04 0.05 0 0.01 0.02 0.03 0.04 0.05
Position (m) Position (m)

Fig. 21. Comparison of solid and gas temperature along the channel for different times throughout cycle for SiC absorber (reduction: t = 0–180 s,
oxidation: t = 180–360 s).

57 0.45
t = 0s
t = 60s
0.4
56 t = 120s
Oxygen Carrier Conversion (-)

t = 180s
0.35
Methane Conversion (%)

55
0.3

54 0.25

0.2
53
0.15
52
0.1

51 0.05

0
50 0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045 0.05
0 20 40 60 80 100 120 140 160 180
Position (m)
Time (s)
Fig. 23. Oxygen carrier conversion along channel during reduction step
Fig. 22. Instantaneous methane conversion during reduction step for SiC
for SiC absorber.
absorber.

such that the decrease in oxygen carrier availability out-

decreasing amount of oxygen carrier available. While the weighs the increase in reactor temperature.
temperature does increase which in turn increases the reac- The methane conversion is mainly limited by the flow
tion rate, the reactor temperatures are already high enough rate/length of the channel (in addition to the solar flux).
 E.J. Sheu, A.F. Ghoniem / Solar Energy 125 (2016) 339–359
Table 4
Overall reactor performance.
Metric Alumina value SiC value
Methane conversion ( gCH 4 ) 54:43% 54:15%
Maximum temperature variation (DT max ) 145:99 K 38:13 K
Solar utilization efficiency (gsu ) 85:15% 85:38%
Chemical efficiency (gchem ) 54:46% 54:41%
Average oxygen carrier conversion (gOC ) 39:20% 36:76%
Thus, the methane conversion can be improved by either
lowering the flow rate or increasing the length of the chan-
nel. However, as discussed previously, an increased length
does not mean more solar energy is absorbed as all of the
solar radiation is absorbed in the front half of the absorber.
For comparison of the conversion with experiments, the
maximum conversion measured from redox studies with
different metals (and comparable reactor temperatures)
range between 50% and 70% (Kodama et al., 2000;
Steinfeld et al., 1998). The cycle average methane conver-
sion evaluated here (54:43%) falls within that range. Note
that the higher end of conversions achieved in experiments
are with more reactive metals such as Tungsten (Kodama
et al., 2000).
The oxygen carrier conversion along the channel at dif-
ferent times during reduction is shown in Fig. 17. Oxygen
carrier conversion increases during the reduction step as it
reacts with more fuel. In addition, the oxygen carrier con-
version is highest at the inlet of the channel due to the higher
temperatures and methane concentration at the inlet of the
channel. The cycle time can be increased to approximately
30 min to achieve very high conversion during reduction;
however, high conversion during reduction is not desired
as this can lead to material degradation over time.
Based on the simulation results, the concentrated solar
flux value used can achieve needed reactor temperatures
for the redox process. The base case channel length is large
enough to achieve conversions comparable to experiments.
The conversion can be improved by increasing the length;
however, increased length could lead to larger temperature
variations which is detrimental long term operation. The
inlet gas temperatures can be increased to also improve
conversion; however, in the context of a hybrid cycle,
increasing the inlet gas temperature for the reformer can
lead to a decrease in overall hybrid cycle performance.
Cycle time can be increased to achieve an higher usage of
the oxygen carrier, but as discussed previously complete
conversion is not desired as that can lead to material degra-
dation over time.
Now that the results for the Alumina absorber have
been discussed, the results of the SiC absorber will be pre-
sented in detail next.
4.2. SiC absorber
As discussed previously, the Alumina absorber experi-
ences large temperature variation throughout the redox
cycle due to the low thermal conductivity which leads to
357
material degradation. Therefore, SiC is also used as an
absorber material because of its higher thermal conductivity.
First, the gas velocity at different points along the chan-
nel throughout the cycle is shown in Fig. 18. Similar to the
Alumina case, the velocity increases along the channel due
to the rising temperature. The velocities in the SiC absorber
are slightly lower than those of the Alumina absorber due
to the lower temperatures experienced by the SiC absorber.
The temperature profiles at different points along the
channel throughout the cycle are shown in Fig. 19. Com-
pared to the Alumina absorber, the SiC absorber experi-
ence less temperature variation along the channel as well
as with time. This smaller temperature variation may be
beneficial in terms of reactor operational stability over long
periods of operation. The SiC absorber reaches a lower sur-
face temperature than the Alumina absorber.
The conduction flux is not as high in the SiC absorber
due to the lower temperature variation (Fig. 20). Also, sim-
ilar to the Alumina absorber, the radiation decays rela-
tively quickly along the channel and is minimal during
oxidation. Again there are two transient states when the
absorber switches between the two reaction steps.
A comparison of solid and gas temperature along the
channel length throughout the cycle is also shown in
Fig. 21. Similar to the Alumina case, the solid and gas tem-
perature are essentially equal at the outlet of the channel.
Overall, the SiC absorber yields a similar methane con-
version to the Alumina absorber because the average tem-
perature within the channel is similar for both cases
(Fig. 22). Similar to the Alumina case, the methane conver-
sion decreases throughout the reduction time as the
amount of oxygen carrier available decreases.
The oxygen carrier conversion along the channel at dif-
ferent times during the reduction is shown in Fig. 23. There
is a more even distribution of oxygen carrier conversion
along the SiC channel due to the more even temperature
distribution. It should be noted that the same kinetic
parameters were used for both the SiC and Alumina case,
but in reality the reaction rates should be different because
of the different support materials.
The overall reactor performance results are summarized
in Table 4. Both absorbers have similar methane conver-
sion and solar utilization efficiency. The similar methane
conversion is due to average reactor temperatures being
nearly the same for both absorbers. Consistent with an
energy balance over the entire cycle, for the solar utiliza-
tion efficiency, the losses are due to the energy required
for heating the carrier gas to the reactor temperatures.
Therefore, since the two absorbers have comparable reac-
tor temperatures, the losses associated with heating the car-
rier gas are approximately the same. Similarly, since the
reactor temperatures and methane conversion are approx-
imately equal, the chemical efficiency is also relatively the
same. The chemical efficiency is lower than the solar utiliza-
tion efficiency as it only accounts for the solar energy used
for reforming rather than both reforming and heating. The
main difference is the maximum temperature variation
358 E.J. Sheu, A.F. Ghoniem / Solar Energy 125 (2016) 339–359
where the SiC absorber has a much smaller temperature
variation which means that it might be more suitable for
long term reactor operation. Therefore, the SiC absorber
can potentially be a better material for this type of reformer
as there is a much smaller temperature variation without a
significant drop in other reactor performance metrics (i.e.,
methane conversion and solar utilization efficiency).
5. Conclusion
Overall, a design for a solar receiver-reactor for steam
redox reforming has been presented. The receiver-reactor
consists of a dumbbell shape absorber system that has
two distinct absorbers. This absorber system setup allows
for the switching between reduction and oxidation steps
without having to constantly change inlet streams to the
reactor. In addition, at any point in time only one solar
absorber is irradiated by the solar energy (during the reduc-
tion step). The receiver reactor is designed such that the
inlet connections do not interfere with the solar window.
A computational model that can help aid in design and
evaluation of reformer performance has also been devel-
oped. The model accounts for mass and heat transfer
between gas and solid phase as well as radiation transport
and conduction through the solid. The model is considered
to be solved when the reformer has reached a cyclic steady
state operation. Using this developed model, two base case
designs were simulated – one with an Alumina absorber
and one with a SiC absorber. The base case results yielded
reasonable results as compared to previous experimental
solar reformer studies. The results show that both absor-
bers strongly absorb the solar radiation and most of the
radiative heat transfer occurs in the front half of the absor-
ber. Therefore, increasing the absorber (channel) length
only contributes to increasing the methane conversion.
The alumina absorber experiences slightly higher reactor
temperatures (especially front face temperatures) than the
SiC absorber; however, average reactor temperature for
both absorbers are approximately the same and thus both
achieve very similar methane conversions. The solar utiliza-
tion efficiency is also essentially the same for both absor-
bers as the average reactor temperatures are similar and
therefore the losses associated with heating the carrier gas
are comparable. Furthermore, the results show that a
absorber material with a higher thermal conductivity might
be better suited for this type of solar reformer in terms of
long term operation.
As discussed previously, many different parameters can
effect reformer performance. For instance, while increasing
the channel length can lead to higher methane conversion
due to longer residence times, it can increase the tempera-
ture variation which is detrimental for long term operation.
Therefore, future work will include performing sensitivity
analysis to determine which design/operating parameters
have the largest impact on reactor performance. By identi-
fying which parameters are most important, the design of
the reactor can be further improved.
Acknowledgments
The authors would like to thank the King Fahd Univer-
sity of Petroleum and Minerals in Dhahran, Saudi Arabia,
for funding the research reported in this article through the
Center for Clean Water and Clean Energy at MIT and
KFUPM under Project number R12-CE-10.
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