Renewable and Sustainable Energy Reviews 59 (2016) 149–159

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Renewable and Sustainable Energy Reviews

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

A review on solar reforming systems

Syed A.M. Said a,n, Mohammed Waseeuddin a, David S.A. Simakov b
a
Department of Mechanical Engineering, King Fahd University of Petroleum & Minerals, Dhahran 31261, Kingdom of Saudi Arabia
b
Department of Chemical Engineering, University of Waterloo, Canada

art ic l e i nf o a b s t r a c t

Article history: Direct combustion of fossils is a low efficiency process that leads to excessive carbon dioxide emissions.
Received 15 January 2015 Highly efficient and clean combustion processes can be achieved by the use of hydrogen as fuel.
Received in revised form Hydrogen can be produced by steam reforming of methane which is a highly endothermic process. Heat
31 August 2015
required for such endothermic process can be achieved by the use of solar energy. The literature indicates
Accepted 16 December 2015
that solar reforming is restricted to high temperature generating solar technologies like solar towers and
dishes due to the high heat demand of the reforming process. A novel idea of using solar parabolic
Keywords: troughs in conjunction with a membrane reformer has been developed which allows low temperature
Methane reforming operation of the process due to the equilibrium shift effect. Molten salt heated in the solar parabolic
Hydrogen
trough facility (up to
600 °C) provides heat needed for the endothermic reforming reactions. In this
Solar energy
review, we provide critical assessment of the latest published developments in solar reforming tech-
Syngas
nologies. We focus on reactor design concepts employed to couple the heat requirements of methane
reforming process with concentrated solar power. The emphasis is novel, alternative routes which have
potential of commercialization.
& 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
2. H2 production via reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
2.1. Reforming methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
2.1.1. Steam reforming of methane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
2.1.2. Dry reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
2.1.3. Partial oxidation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
2.1.4. Autothermal reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
2.2. Catalysts for reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
2.3. Recent numerical work in steam reforming of methane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
3. Reforming using solar energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
3.1. Indirectly heated reformer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
3.2. Tubular reformer–receiver . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
3.3. Windowed/Volumetric reformer–receiver . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
3.3.1. ASTERIX experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
3.3.2. Directly irradiated annular pressurized receiver (DIAPR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
3.3.3. Thermochemical receiver/reactor system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
3.3.4. CAESER experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
3.3.5. The Weizmann Institute reactor/receiver . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
3.3.6. Sodium reflux reformer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
3.3.7. Dry reforming using FeO catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
4. Potential for solar parabolic troughs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
4.1. Numerical and experimental works on membrane reformers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
4.2. Coupling membrane reformers to solar parabolic troughs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157

n
Corresponding author. Tel.: þ 966 13 8603123; fax: þ966 13 8602949.
E-mail address: samsaid@kfupm.edu.sa (S.A.M. Said).

http://dx.doi.org/10.1016/j.rser.2015.12.072
1364-0321/& 2015 Elsevier Ltd. All rights reserved.
150 S.A.M. Said et al. / Renewable and Sustainable Energy Reviews 59 (2016) 149–159
5. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
1. Introduction
The energy sector worldwide is largely dominated by the
burning of fossil fuels which leads to the emissions of CO2 into the
atmosphere and is known to contribute to the undesired global
warming. It is generally accepted that the increase in the tem-
perature of the earth is linked to the increase in greenhouse gases,
mostly CO2, in the atmosphere. CO2 is a major greenhouse gas
released whenever fuels containing hydrocarbon, such as
methane, are burned [1]. Most of the world's energy needs are
currently met by combustion of hydrocarbon fuels. The use of
renewable energy is an alternative which has potential to provide
a favorable solution to the problem of greenhouse gases emissions.
But the current cost of technologies based on renewable energy is
currently competitive enough to fossil fuels based technologies
and more advancements are still required.
Fossil fuels are heavily used in power industry as it is relatively
cheap and abundant. Various current estimates place the world
peak for fossil fuel consumption between 2009 and 2035 [2],
implying that there is at least as much oil still available in the
world as has been consumed since the industrial revolution. The
discovery of methane hydrates in vast quantities indicates that
fossil fuel will continue to be used for decades to come. Unfortu-
nately combustion of these fuels produces pollutants and CO2, the
main contributor to global warming. One of the main challenges
facing engineers now is how to reduce or prevent the negative
impact of CO2 emissions due to burning of fossil fuels on the cli-
mate, while allowing the continued use of fossil fuels for power
production.
Carbon capture and sequestration (CCS) means capturing CO2
and trapping it away from the atmosphere. There are many
methods of sequestering CO2 either by utilization in industrial
processes or by storage underground or in deep seas. Enhanced Oil
Recovery (EOR) is another option which involves injecting CO2 into
partially depleted oil wells to increase oil production. This is cur-
rently common practice in many oil companies. CO2 is also utilized
in Enhanced Coal Bed Methane Recovery (ECBM) for harvesting
methane from unmineable coal by injecting CO2 into the coal bed.
The neutralization of alkali pollutants can be done by using CO2 in
polluted areas. Yet another method is to absorb CO2 into coal beds
that are inaccessible and cannot be mined. Some minerals will
react with CO2 to form a solid product. There are two methods of
doing this; the first is mining the reactant mineral and the second
is reacting it with CO2 to produce a product which can be used in
road pavement, or injecting CO2 into subterranean caverns con-
taining the reactant mineral, and allowing it to slowly react over
time. Other methods of CO2 storage include injection into some
geological formations, particularly porous rock.
Many methods have been proposed for capturing CO2 produced
by combustion of fossil fuels for production of electricity. The fuel
may be burned in air, and the exhaust products separated to
capture CO2. This usually involves either cryogenic or chemical
processes, or use of membranes to separate gases. These methods
are costly and consume a large amount of energy, thus resulting in
reducing the power plant efficiency. Since it is now necessary to
look for a clean energy source, the available choices are hydrogen
and green solutions. The carbon is removed from hydrocarbon fuel
before combustion, by conversion of methane to syngas, a mixture
of carbon monoxide (CO) and hydrogen (H2), followed by
separation of H2 from the mixture. This process is called reform-
ing, being the oldest, cheapest and most widely used method to
produce hydrogen commercially worldwide [3]. It is possible to
produce pure H2 by this method, which is an energy rich fuel
source. Hydrocarbons usually used for hydrogen production are
natural gas, liquid gas, naphtha, coal and methane among which
methane is highly used due to its high hydrogen content and low
capital costs as compared to other hydrocarbons.
Methane reforming is highly endothermic that requires large
heat inputs. In industrial plants, reformer tubes packed with cat-
alyst pellets are heated (typically to temperatures of 850–950 °C)
by burning a fraction of natural gas (ca. 30%). An attractive alter-
native is to use concentrated solar energy to provide the heat
required to drive the reaction, thus saving the otherwise com-
busted fraction of the natural gas. The resulting ″solar fuel″, which
contains solar energy stored in chemical bonds, can be used for
either electricity generation in gas turbines or as a chemical
feedstock. There are a number of recent reviews on solar ther-
mochemical conversion which discuss thermodynamics and
kinetics [79], catalysis [79], system design [80] and various ther-
mochemical conversion routes [81]. Herein, we specifically focus
on natural gas reforming and provide critical assessment of the
latest developments in solar thermal reforming technologies. The
emphasis is on solar reformer design concepts and on alternative
designs which can eventually allow widespread commercialization
of solar thermochemical conversion technologies.
2. H2 production via reforming
2.1. Reforming methods
2.1.1. Steam reforming of methane
Since steam reforming of methane produces syngas with the
highest hydrogen to CO ratio, it is considered to obtain highly pure
hydrogen. The overall process of steam reforming of methane can
be described by the following reactions (steam reforming, water
gas shift and overall reaction):
CH4 þH2 O⇄CO þ3H2 ð1Þ
CO þH2 O⇄CO2 þ H2 ð2Þ
CH4 þ2H2 O⇄CO2 þ 4H2 ð3Þ
The overall process is highly endothermic which requires large
amounts of heat for the process to take place. In a conventional
plant, the required heat is typically provided by combusting a
fraction of natural gas (up to
30%) to fire the reformer tubes
packed with catalyst from outside, while another fraction is fed to
the reformer tubes. The CO produced by the SMR reaction is
reacted with steam in downstream reactors to produce more
hydrogen by water gas shift (WGS).
Being an endothermic process, steam reforming requires very
high temperatures and makes the process expensive. However,
alternative processes of methane reforming are being studied to
gain economic viability according to the requirement of syngas
produced. The concern with the economic viability lead to the
development of alternative processes of methane reforming,
which are dry reforming, partial oxidation and autothermal
 S.A.M. Said et al. / Renewable and Sustainable Energy Reviews 59 (2016) 149–159
reforming which are being studied by researchers for producing
syngas [4–6].
2.1.2. Dry reforming
Dry reforming is a process which produces syngas; with
hydrogen to CO ratio of 1. In this process, methane is reacted with
carbon dioxide in the presence of a catalyst, to produce syngas
[4,7]. The dry reforming of methane reaction is given as:
CH4 þ CO2 ⇄2CO þ 2H2
This reforming process is considered when the produced syn-
gas is used for the material synthesis of fuel liquids and requires
syngas as raw materials. Coke, which is deposited on the surface of
the catalyst, reduces the activity of the reaction and is considered
as a disadvantage of dry reforming as it reduces its useful life. Coke
formation is due to the presence of CO2 as a reagent in the reac-
tion. Thus, dry reforming is a unique process of methane reform-
ing that is affected by two reagents that contain carbon (CH4 and
CO2) [4,8,9]. There is likely more chances of coke formation in this
process due to the low H/C ratio when compared to steam
reforming [8]. Low coke formation rate on the catalyst surface is
one of the main challenges for dry reforming for which active
catalysts need to be developed. Use of supports which favor the
dissociation reaction of CO2 into CO and O can reduce the coke
formation to some extent [9].
2.1.3. Partial oxidation
Another method for production of syngas is the partial oxida-
tion of methane in which methane reacts with oxygen in the
presence of a catalyst. The resultant syngas obtained by this pro-
cess is of good hydrogen to CO ratio [10]. The reaction for partial
oxidation of methane is expressed as:
1
CH4 þ O2 ⇄CO þ 2H2
2
Since partial oxidation of methane is an exothermic process
and requires a lower amount of thermal energy, it is considered to
be economical compared to other reforming processes. From
another point of view, the process is considered expensive as it
requires a flow of pure oxygen for combustion of methane. Specific
care must be taken during the process since the two reagents
involved (CH4 and O2) are highly explosive and may prove to be
dangerous [11].
2.1.4. Autothermal reforming
Steam reforming and partial oxidation methods were com-
bined to give a new process to produce syngas namely Auto-
thermal reforming. Thus, in the steam reforming there is contact
with a flow of gaseous oxygen, in the presence of a catalyst [5]. The
three reagents for autothermal reforming of methane are CH4, H2O
and O2. The thermal energy required for the steam methane
reforming process is generated by partial oxidation and thus saves
a significant amount of energy. Since the produced syngas con-
sumes the thermal energy it generates, it is named autothermal
[12]. Hydrogen to CO ratio in the syngas depends on the gaseous
reactant fractions introduced in the process. A value of H2/CO ratio
ranges between 1 and 2 [13].
Overall, methane reforming is an important process in the
energy sector for the conversion of natural gas into highly pure
hydrogen. The ultimate purpose of methane reforming is to obtain
high-purity gaseous hydrogen; however, the type of method used
in the conversion process of methane in syngas influences on H2/
CO ratio obtained. According to the authors of [5,6,14] main type of
reforming processes of methane is the steam reforming process,
because it generates syngas with the highest H2/CO ratio. The
product obtained from the reforming process is a fuel which is
151
considered ideal for the development of catalytic processes to
obtain high-purity gaseous hydrogen and to be used as feedstock
in the petrochemical industries to produce liquid fuels and
methanol. However, alternative methods for natural gas reforming
were developed with the aim of making savings in thermal energy
consumption; steam reforming method is found to be an efficient
one for bulk hydrogen production. Thus, the choice of the most
appropriate catalytic chemical process of methane reforming
should account for the economic viability of the process with
ð4Þ
regard to the purpose given to the syngas produced. In other
words, it can be said in short that the choice of the chemical
process of reforming to be used in the conversion of methane in
syngas should be made based on the final application that will be
given to syngas obtained. Partial oxidation, dry reforming and
autothermal reforming can also serve as options to produce syn-
gas, nevertheless depending on the value of H2/CO ratio to be
obtained, especially when it comes to reduce the consumption of
thermal energy, one of the most important factors in the imple-
mentation of an industrial project.
The cost of syngas produced by means of the steam reforming
of methane process is directly dependent on natural gas prices and
is found to be one of the least expensive methods among all bulk
hydrogen production technologies. It is a common fact that natural
gas is readily available around the world and thus hydrogen gen-
eration by means of steam reforming becomes very attractive.
Steam reforming of methane is widely used in industry today
wherein hydrogen is produced in large centralized plants for use
in numerous applications, including chemical manufacturing and
petroleum refining. Research and development is currently con-
cerned with the development of small-scale technologies for
steam reforming of methane to enable distribution of hydrogen
and improve delivery infrastructure [15]. Regardless of the type of
reforming process employed in syngas production, it is important
ð5Þ to emphasize that the success of the conversion of methane is
strongly dependent on the catalytic system used in the process, as
well as on operational conditions such as reaction temperature. In
this case one should always have in mind that the catalytic system
is the material that activates the conversion reaction of methane.
One of the appropriate reforming process which produces hydro-
gen on a large scale using a nickel based catalyst is steam
reforming. Nickel being easily available and relatively cheaper than
other metal catalysts, attracts researchers towards the study and
development of steam reforming.
2.2. Catalysts for reforming
Steam reforming uses nickel based catalysts as the active
material. However, cobalt and other noble metals also catalyze the
steam reforming reaction but are generally too expensive to find
widespread use. Ruthenium and Rhodium have higher activity per
metal area than nickel but are usually not considered due to their
high costs being rare earth metals. A number of different carriers
including alumina, magnesium–aluminum spinel, and zirconia are
employed. Some of the problems faced by SMR process are low
methane conversion due to reversibility, coke formation, catalyst
deactivation, heat transfer issues and diffusion limitations [16–18].
Being catalytically promoted, the process is sensitive to the cata-
lyst used not only chemically but also due to the physical phe-
nomena taking place. Thus, complete insight of the phenomena is
necessary to run the process efficiently and economically.
As mentioned, the most commonly used catalyst for steam
methane reforming (SMR) is nickel. Ni is used unsupported as well
as supported on certain supports such as SiO2, Al2O3, Al2O4, ZrO2,
Ce–ZrO2 [19–23]. Low conversion, deactivation and coke formation
are issues that makes certain catalysts unsuitable for the SMR
process since in real life, reformers operate far away from ideal
152 S.A.M. Said et al. / Renewable and Sustainable Energy Reviews 59 (2016) 149–159
conditions. Usually operating pressure are set very high as
required in synthesis loop but at the same time, reduce conver-
sion. The presence of higher hydrocarbons and sulfur content
along with high pressure make the environment severe for the
catalyst. Ni supported on certain supports such as Al2O4, Al2O3 and
SiO2 were reported to be deactivated severely due to oxidation of
Ni [24]. It was found that NiAl2O3 [25] catalyst deactivated
severely even when operated under different reaction systems to
check the dependence of heat transfer mechanism [26]. Also,
pretreatment of the catalyst with other metals like Rh was found
to give higher activity also at elevated temperatures after under-
going certain oxidation reduction reactions for Al2O3 [23].
A comparative study of Ni supported over Ni/Ce–ZrO2, Ni/ZrO2,
Ni/CeO2, Ni/MgAl2O4 and Ni/Al2O3 [27] indicated that Ni over Ce–
ZrO2 catalyst have higher activity due to high interaction between
Ni and Ce–ZrO2 supports and also due to high oxygen carrying
capacity. In another study, Ni/Ce–ZrO2θ–Al2O3 catalyst was tested
against the steam treatment effects and it was found that catalyst
deactivated in steam due to formation of inactive Ni–Al2O4
reduced to Ni and Al2O3 in presence of H2. Same effect was
reported to be the reason for the deactivation of Ni–Al2O3 catalysts
but this deactivation was low due to the coverage provided by
ZrO2. Thus, the catalyst was found to be highly active by using low
steam concentrations in the reactor feed initially so that the pro-
cess proceeds in the forward direction and some hydrogen is
produced [24].
Since steam methane reforming occurs on the surface of the
catalyst (surface reactions), increasing the amount of active metal
will increase the surface area for species to absorb resulting in
higher reaction rates. However, the loading of active metal is
limited due heat and mass transfer effects. Ni loading on reduced
NiAl2O3 catalyst was optimized to 12% within a range of 6–15%
loading and also it was reported that below 3% loading of Ni,
inactive Ni Al2O4 is formed. Also, reduction of the catalyst makes it
liable for higher conversion and thus conversion of 80% was
reported at atmospheric pressure, temperature of 1023 K and S/C
of 1 [28].
Sintering is another problem associated with the steam
reforming catalyst. It is the loss of surface area of the active species
of the catalyst due to migration and coalescence of nickel particles
on the carrier surface and is a complex process influenced by
several parameters including chemical environment, catalyst
structure and composition [29–33]. Factors like high temperature
and high steam partial pressure enhance sintering. Also, steam
reforming catalysts are susceptible to sulfur poisoning. At steam
reforming conditions, all sulfur compounds are converted into
hydrogen sulfide, which is chemically absorbed on the nickel
surface, enhancing the phenomena. It is reported that for Ni
supported over MgAl2O4 catalyst, sintering occurs in the initial
200 h of the reaction, after which, change in the size of Ni particles
is small. The size of the nickel particles is limited after sintering
and is related to the support surface area and Ni loading yielding
to sintering being proportional to nickel loading [34]. The sintering
process is more affected by temperature than time and at higher
temperatures, particle migration is dominant whereas atomic
migration dominates at low temperatures [35]. The operating
conditions in a reformer depend on the type of feedstock and the
application. The typical inlet temperature is between 350 °C and
550 °C. The selection of the operating conditions is in many cases
dictated by the limits of carbon formation on the catalyst. For a
given feedstock and pressure, the reformer must be operated
within a certain temperature window. The formation of a whisker
type of carbon will occur above the upper temperature limit
whereas operation below the lower temperature limit may result
either in a polymeric type of carbon formation (gum) or lack of
sufficient catalyst activity.
2.3. Recent numerical work in steam reforming of methane
There has been an extensive work on the numerical analysis of
the steam reforming in order to study and improve the process.
Seo et al. [36] numerically investigated a reforming system con-
sisting of a combustion zone and Steam Methane Reforming (SMR)
and Water Gas Shift (WGS) bed. The numerical results from the
analysis were found to be in good agreement with the experi-
mental values. Concentration of the species at the exit, tempera-
ture in the WGS bed, heat transfer to the catalyst bed and the
steam methane reforming reactions were studied depending on
the operating parameters. Also, analysis was made on the outer
wall of the system by providing a cooling flux, effect of which
reduced the methane conversion and carbon monoxide yield in
the SMR bed. Increasing steam to methane ratio showed increase
in the methane conversion along with a decrease in the carbon
dioxide concentration. Zhai et al. [37] developed a simulation
model for the steam methane reforming reaction in a micro
reactor consisting of a combustion channel and a reaction channel.
The SMR reaction was Rh-catalyzed whereas the combustion was
Pt-catalyzed. The CFD model built included the elementary reac-
tion kinetics for the SMR reactions and global reaction kinetics was
applied for combustion. Heat conduction ability of the wall was
given importance in the study which affects the interplay between
the endothermic and exothermic reactions occurring simulta-
neously in the reactor. A characteristic value of 0.5 mm was sug-
gested by the authors for the thickness of the walls. A simulation
study on the Zone Flow Reactor was done by Wilde and Froment
[38]. Zone Flow is a tubular reactor having two types of internals: a
core type and a casing type which is adjacent to the wall, having a
thin layer of catalyst over them. A very complex reactor with
corrugations, blades and cones was studied in order to improve
the heat transfer. Higher catalyst efficiency per unit reactor
volume was achieved due to the higher geometric surface area.
Also, a judicious design for the relative position of the internals
and their geometrical characteristics and higher catalyst effec-
tiveness, higher energy efficiency and lower steam to carbon ratios
was aimed in the study. Irani et al. [39] did numerical analysis of
the steam methane reforming reactions in a monolith reactor
using surface based and volume based reaction models. In the
surface based approach, the reaction takes place near the wall
where the catalyst is coated whereas reaction of chemical species
through penetration inside a thin catalyst layer occurs in a volu-
metric approach. The numerical models developed utilized the
Langmuire Hinshelwood type of kinetic reaction rates for the SMR
and Water Gas Shift reactions. The modeling results of the surface
based reactions were found to be more accurate with the experi-
mental data. However volumetric reaction models are of good
choice as long as they predict the experimental data closely.
Pantoleontos et al. [40] studied the steam reforming of methane in
a packed bed reactor considering the dynamic behavior of the
process. A set of partial differential equations were developed and
validated against experimental results for the physico-chemical
process. The physico-chemical process taking place in the solid
and gaseous phase were set to the operating conditions of an
actual reformer with high temperatures and pressures. The heat at
the reactor wall was optimized for hydrogen yield. The dynamic
conversion, temperature and partial pressures profile at the bed
and particle level were well demonstrated by the use of 2-phase
reactor concept and optimized wall temperature profile.
Butcher et al. [41] presented a study on a bench-scale annular
microchannel reactor (AMR) prototype for the endothermic steam
reforming of methane. The experimental results at a steam to
methane ratio of 3, reactor temperature of 1023 K, and pressure of
11 bar showed catalyst power densities of 1380 W per cm3 and
hydrogen yields greater than 98% of thermodynamic equilibrium.
 S.A.M. Said et al. / Renewable and Sustainable Energy Reviews 59 (2016) 149–159
Also, a two-dimensional steady-state computational fluid dynamic
model was developed and validated using experimental data to
identify suitable operating conditions for mass production AMR.
Thermal efficiencies, defined based upon methane and product
hydrogen higher heating values (HHV's), of 72.7% and 57.7% were
obtained from simulations for methane capacities of 0.5-2S LPM at
hydrogen yields corresponding to 99–75% of equilibrium values.
Further, the analysis of local composition, temperature and pres-
sure indicated that catalyst deactivation via coke formation or
nickel oxidation was not thermodynamically favorable. Mondal
et al. [42] worked on the economic and environmental analysis of
thermocatalytic decomposition of methane (TCDM) – a process
that decomposes methane thermally to produce hydrogen from
natural gas. Although, TCDM is not yet commercial, it may prove to
be competitive with the more popular SMR process due to its
lower carbon footprint. The low temperature (600 °C) operation of
the process (TCDM) could lead to a significant energy and methane
gas saving when compared to the conventional steam reforming.
Angeli et al. [43] studied the effect of presence of higher alkanes in
the natural gas feedstock on carbon accumulation during low
temperature steam reforming of methane. The feedstock was
investigated over Ni and Rh catalysts supported on lanthanum
doped ceria–zirconia mixed oxide. Both catalysts showed high
resistance to coke formation and especially in the case of Rh/La/
CeO2–ZrO2, the carbon accumulation detected was low even after
10 h on stream in steam reforming of all mixtures of hydrocarbons
tested. The presence of higher alkanes in methane increased the
amount of carbon on Ni compared to pure methane as well as the
nature of the carbonaceous species. Increase in the C-number of
the additive alkane had almost no influence on the total amount of
carbon formed but favored the formation of filamentous carbon.
3. Reforming using solar energy
Research in the last two decades has demonstrated the efficient
use of solar thermal energy for driving chemical reforming reac-
tions [44–53]. In these highly endothermic reactions, hydro-
carbons are reacted with steam or carbon dioxide (CO2) over a
catalyst to form a synthesis gas (syngas) composed primarily of
hydrogen (H2) and carbon monoxide (CO). The solar heat is
applied to the reactor either indirectly through a working fluid
(such as air heated in a solar receiver) or directly via reactor tubes
or a porous catalytic reactor exposed to concentrated solar radia-
tion. In open-loop systems, a hydrocarbon feedstock (e.g., natural
gas, pyrolized or gasified coal or oil shale, or low-quality hydro-
carbon gases or waste) is upgraded in energy content with solar
energy. In closed-loop systems, a high-quality hydrocarbon feed-
stock such as methane (CH4) is converted to syngas via solar
reforming; the syngas is then stored or transported off-site prior to
conversion back to CH4 in a methanation reactor that recovers the
solar energy as heat or industrial processes for power generation.
The high temperatures required for solar reforming effectively
limit the concentrator choices to solar dishes and central receivers.
The dish technology is modular and is well suited to distributed
applications such as the destruction of toxic wastes. On the other
hand, bulk energy production, whether in closed-loop or open-
loop configuration, probably must be carried out on a large scale to
compete with fossil fuels and probably requires the tower (central
receiver) technology. In recent years, several basic solar reformer
concepts have been investigated. These reformers can be classified
as the indirectly heated reformer, the tubular reformer–receiver,
and the windowed or volumetric reformer–receiver [54].
153
3.1. Indirectly heated reformer
The indirectly heated reformer consists of a tube bundle con-
taining catalyst within the tubes through which the process gas is
circulated, and heated by a secondary fluid that gets its thermal
energy from a solar receiver [45]. Heating agents that have been
considered are air, helium and condensing sodium vapor. The
indirectly heated steam reformer has potential advantages of uti-
lizing commercially proven tubes and catalyst, and can be equip-
ped with thermal storage or auxiliary fossil firing to give extended
or 24-h operation. This mode of operation is desirable to reduce
capital costs and provide a uniform product. The process pressure
can be optimized independent of the solar receiver pressure. On
the other hand, the indirectly heated system has more equipment,
and the secondary fluid introduces additional pumping and tem-
perature losses.
3.2. Tubular reformer–receiver
The tubular reformer/receiver incorporates the catalyst-bearing
tubes directly into the solar furnace where they are heated by solar
radiation [51]. While this concept eliminates the costs and energy
losses associated with the secondary heat transport loop, a larger
and more costly solar receiver is required. A limited amount of
heat storage is associated with the receiver, sufficient to damp the
effect of solar transients. Auxiliary fossil-fuel or electrical heating
can be used to extend the heating time, and there is freedom in
selecting the optimal process pressure.
3.3. Windowed/Volumetric reformer–receiver
The windowed or volumetric reformer/receiver places the
reforming catalyst in a position where it is heated directly by the
solar beam, making very high volumetric reaction rates possible
[46]. As a result, the receiver is quite compact and potentially
inexpensive. However, this technology requires good matching of
flow rate with solar flux and also the development of reliable
windows (which may limit operating pressure) and does not lend
itself to energy storage or non-solar operation. Nevertheless,
prospects for low capital costs and a good match to dish con-
centrators make this concept attractive. The individual receiver
cells are limited in capacity by the window area, but large modular
arrays are feasible for solar towers.
3.3.1. ASTERIX experiment
ASTERIX [44,45] experiment for solar steam reforming of
methane was conducted in the early 90's for investigating the
details and problems associated with the process heat demand for
an industrial chemical process with solar-generated high tem-
perature heat, using an indirectly heated reformer. The specific
objectives of the ASTERIX experiment were to collect and store an
optimum amount of solar energy, to obtain maximum conversion
of methane and to produce consistently high-quality synthesis gas.
A Gas-Cooled Solar Tower (GAST) system [45] was used to produce
hot air and drive a separate steam reformer which was again fed
into the GAST cycle. Results of the test were found to be more
temperature dependent in comparison with pressure achieving
93% methane conversion at 803 °C and 6 bar pressure. Fig. 1 shows
the schematic of the reformer reactor used in ASTERIX study.
3.3.2. Directly irradiated annular pressurized receiver (DIAPR)
A DIAPR system which uses steam reforming of methane with a
Ru/Al2O3 catalyst promoted by Mn oxides was studied by Berman
et al. [46]. A directly irradiated annular pressurized receiver
reactor (Fig. 2) was used as the receiver reactor which was used in
conjunction with a field of heliostats. The absorber of the receiver
154 S.A.M. Said et al. / Renewable and Sustainable Energy Reviews 59 (2016) 149–159
Fig. 1. Cross-section of ASTERIX [45] heat exchange reformer.
Fig. 2. Schematic of DIAPR solar facility [46].
consisted of pins arranged in the shape of a porcupine made of
sintered alumina (99.7% Al2O3). The catalyst activity and stability
was tested for methane conversion at different reforming tem-
peratures ranging from 500–1100 °C using fresh catalyst and cat-
alyst that has been used for 506 h at 1100 °C. It was found that the
Fig. 3. Experimental set up of DeMaria et al. [47].
activity of the catalyst does not change significantly even after
prolonged use which suggested that the catalyst was thermally
stable. The same tests when conducted with the same catalyst but
without Mn oxides showed that the activity of the catalyst
decreases drastically at higher temperatures.
3.3.3. Thermochemical receiver/reactor system
A receiver reactor paired with a solar furnace with heliostats to
collect the solar radiation and reflect it onto the parabolic reflector
was studied by De Maria et al. [47,48]. The catalyst used in this
study was 10% Ni deposited on Al2O3 pellets. The reformer was
tested for different steam to methane ratios (1–3) and tempera-
tures (680–750 °C) at atmospheric pressure. It was found that at
the highest temperature studied (750 °C), methane conversion
was within 20% of the equilibrium and the heating value of the
product gases was approximately 20% higher than that of the input
methane. The experimental setup of this study is shown in Fig. 3.
3.3.4. CAESER experiment
The CAtalytically Enhanced Solar Absorption Receiver (CAESAR)
[49,50] test was conducted to determine the thermal, chemical,
and mechanical performance of a commercial-scale, dish moun-
ted, direct catalytic absorption receiver (DCAR) reactor over a
range of steady state and transient (cloud) operating conditions.
The focus of the test was to demonstrate “proof-of-concept” and
determine global performance such as reactor efficiencies and
overall methane conversion. The objectives of the project were to
demonstrate the solar DCAR concept using a commercial-scale
receiver/reactor on a parabolic dish, and to develop numerical
simulation models capable of predicting the global performance of
the receiver/reactor unit and the thermal, chemical and mechan-
ical performance of the absorber. The focus, therefore, was on
obtaining global and absorber performance data over a range of
steady-state and transient operating conditions (e.g., cloud tran-
sients) and comparing these results with model predictions. The
system was operated during both steady-state and solar transient
(cloud passage) conditions with total solar power absorbed value
of 97 kW and maximum CH4 conversion of 70%. Receiver thermal
efficiencies ranged up to 85% and chemical efficiencies peaked at
54%. Global model predictions such as reactor efficiencies and CH4
conversion compared well with test data. For example, model
predictions of 71.9%, 48.2%, and 46.5% for thermal efficiency, che-
mical efficiency, and CH4 conversion, respectively, for one of the
CAESAR tests, compared favorably with the corresponding test
values of 79.3%, 50.7%, and 45.9%. Fig. 4 shows a pictorial of the
CAESER unit.
 S.A.M. Said et al. / Renewable and Sustainable Energy Reviews 59 (2016) 149–159
Fig. 4. The CAESER Unit [50].
Fig. 5. The Weizmann Institute 480 kW reformer/receiver [51].
3.3.5. The Weizmann Institute reactor/receiver
A 480 kW testing facility of reformers was developed at
Weizmann Institute of Science [51]. A solar receiver with storage
and transportation, for development of high temperature tech-
nology was designed for both carbon dioxide (CO2) and steam
reforming. The test facility (shown in Fig. 5) operated between 1 to
18 bar pressure, coupled with a methanator system that recovers
the heat energy from the reverse reaction. The cavity receiver
contained eight vertical reformer tubes (2-in. schedule 80), 4.5 m
long (active length). The overall dimensions of the device were
about 5 m high, 4.5 m wide and 3 m deep. The reactor was
designed to produce syngas at 800 °C which resembled commer-
cial reformers except that a solar cavity receiver had replaced the
conventional gas-fueled radiant furnace.
3.3.6. Sodium reflux reformer
Another chemical reactor was integrated into a sodium reflux
heat pipe receiver for carbon dioxide reforming of methane and
tested in the solar furnace of the Weizmann Institute of Science
[52]. The receiver/reactor was a heat pipe containing seven tubes
inside an evacuated metal box containing sodium as shown in
Fig. 6. Two of the tubes were filled with catalyst, 0.5 wt% Rh on
alumina and the front surface of the box served as the solar
155
Fig. 6. Sodium heat pipe reformer [52].
Fig. 7. Dry reforming using FeO as catalyst setup [53].
absorber. In operation, concentrated sunlight heated the front
plate and vaporized sodium from a wire mesh wick attached to the
other side of the plate. Sodium vapor condensed on the reactor
tubes, releasing latent heat and returning to the wick by gravity.
Adequate performance of the receiver system was observed during
many tests under varying flow conditions. The maximum power
absorbed was 7.5 kW at temperatures above 800 °C. The feasibility
of operating a heat pipe receiver/reactor under solar conditions
was proven, and the advantages of reflux devices were confirmed
in this study.
3.3.7. Dry reforming using FeO catalyst
To convert solar energy into chemical energy, an infrared fur-
nace was designed and tested with FeO powder as catalyst for the
dry reforming of methane [53]. The FeO powder was suspended in
a molten salt solution wherein the reactants were flown and
observed at different flow rates. It was observed that the product
consisted of CO, H2 and H2O with a ratio of 3:1:1 respectively at a
flow rate of 200 ml/min and that of CO and H2 with a 2:1 ratio at a
flowrate of 50 ml/min. Theoretical dry reforming of methane was
attained at a flowrate of 50 ml/min due to the contact efficiency
between the catalyst (FeO powder) and CH4/CO2 mixed gases. This
experiment of methane reforming reaction with CO2 also
demonstrated the use of FeO as catalyst in the molten salt medium
for converting solar into chemical energy. The experimental setup
of this study is shown in Fig. 7.
156 S.A.M. Said et al. / Renewable and Sustainable Energy Reviews 59 (2016) 149–159

Table 1 summarizes the solar reforming experiments con- Among various technologies related to production, separation
ducted by various researchers in the past few years and shows and purification of H2, membrane reactor technology seems to be
particularly the type of solar facility and catalysts used in promising and membrane separation assisted reforming is nowa-
their study. days increasingly considered as a good candidate for substituting
conventional systems [58]. The specific thermodynamic constrains
limiting traditional reactors can be circumvented by using inno-
vative integrated systems, such as the membrane reactors (MRs),
4. Potential for solar parabolic troughs
systems in which both reaction and separation are carried out in
the same device. Basically, membranes are barriers which allow
Economic viability of the process equipment should also be
the flow of a specific component in the gas stream to the other
considered while applying the solar facilities like solar towers and
side. The permeated component is known as permeate while the
dishes for performing solar reforming. Also there is a higher
retained mixture is the retentate. High selectivity, high flux, low
probability of heat losses to the environment when working with
higher temperatures, thus making the process inefficient. In cost and high mechanical and chemical stability are some of the
characteristics which a separation membrane should possess.
addition, capital cost investments should be made on thermal
With the use of perm-selective membranes, it is possible to
insulations which restrict the heat losses from the solar facility
perform steam reforming of methane reactions at lower tem-
(towers and dishes) to the reactor. Another mature and relatively
peratures than the conventional ones. This is done by removing
inexpensive solar technology is the solar parabolic trough, but the
the hydrogen formed from the products stream, shifting the
temperatures obtained (max. 600 °C) are not sufficient for the
equilibrium towards the product side and promoting the reaction
reforming process and thus solar reforming using solar parabolic
kinetics according to Le Chatelier's principle. The removal of
troughs technology is not investigated in the past. Although solar
hydrogen is done by use of membranes which are highly selective
parabolic troughs do not generate the temperatures required for
to hydrogen within the vicinity of the reactor. Dense metal
reforming (850–950 °C), this technology can be applied for solar
membranes like Pd and its alloys are currently the most suitable
reforming processes by developing a reformer which operates at
due to remarkably high hydrogen selectivity. Recent developments
lower temperatures than those required for traditional, indust-
in Pd and Pd alloy membranes [59,60] allow the use of these
rially practiced reforming (Fig. 8).
membranes to a temperature range of 300–700 °C. The Pd-based
Table 1 membranes which characterize the high hydrogen selectivity fol-
Comparison of different solar reforming systems. low a solution diffusion mechanism. The hydrogen flux across the
membrane is governed by Sivert's Law [61] according to which the
Author Solar facility Catalyst Temperature (oC) Conversion
flux across the membrane is proportional to the difference of the
ASTERIX Solar tower N/A 702–803 91 square root of hydrogen partial pressures at the two sides of the
[44,45] membrane. Sivert's law is given by:
CAESER [49,50] Solar dish Rh–Al2O3 750–1100 66
 
TCRR [47,48] Solar furnace Ni-Cr 650–850 60
EH  0:5 
Kodama et al. Xe Arc lamp Ru/γ–Al2O3 730–1030 73 J H2 ¼ AH2 exp  2 pH2 p0:5
H 2 ;M ð12Þ
[55] Rg T
Levy et al. [56] Solar furnace Rh–Al2O3 700–900 67
Gokon et al. Infrared FeO 900–950 70 where, JH2 is the hydrogen flux, AH2 is the pre-exponential factor,
[53] furnace
PH2 and PH,M are the partial pressures of hydrogen at the feed and
Dahl et al. [57] Solar furnace No catalyst 1770–1860 77
permeate side.

Fig. 8. Simplified scheme of the reformer heated by solar parabolic troughs.

 S.A.M. Said et al. / Renewable and Sustainable Energy Reviews 59 (2016) 149–159
4.1. Numerical and experimental works on membrane reformers
Uemiya et al. [62] compared the SMR performance of a sup-
ported Pd membrane and a porous Vycor glass membrane in a
membrane reactor in a temperature range of 623–773 K. While the
Pd membrane efficiently exceeded the equilibrium conversion,
only a small change in equilibrium was observed for porous Vycor
glass. Simakov and Sheintuch [63] provided experimental
demonstration of the autothermal Pd membrane reformer and
studied the effects of various parameters on the reformer perfor-
mance. It was shown that the reactor performance is strongly
affected by the ratio of the feed rate to the maximal H2 separation
rate (membrane area and permeability). Chibane and Brahim [64]
studied a one dimensional model of a Pd membrane reactor for
SMR, evaluating the reactor performance in terms of CH4 conver-
sion, H2/CO ratio and H2 recovery. The reactor performance was
found to be optimal (nearly complete conversion and high H2
recovery) for the temperature range of 580–600 °C, steam-to-
methane ratio of 3, pressure range of 300–600 kPa and a sweep
gas ratio of 3. In another simulation study conducted by Fernandes
and Soares [65], it was shown that the membrane thickness is an
important parameter in the membrane reactor performance and
that the use of ultrathin membranes (μm scale) can significantly
enhance methane conversions. Simakov and Sheintuch [66]
defined a one dimensional non-isothermal model of the auto-
thermal Pd membrane reformer and studied systematically the
effects of various design and operation parameters on the reformer
performance. The simulations mapped the acceptable domain of
operation and the optimal set of operating parameters. A novel
hybrid plant for the production of a mixture of methane and
hydrogen (17 vol%) from a steam-reforming reactor whose heat
duty is supplied by a concentrating solar power (CSP) plant by
means of a molten salt stream was demonstrated by De Falco et al.
[67]. The results showed that a CSP plant with an active area of
about 16,000 m2 coupled with a tube-and-shell reactor, with four
reformers is able to supply the electricity and enriched methane to
about 2930 domestic users.
Numerical simulations of membrane using finite-volume
approach are very few. In the numerical work done by Marin
et al. [68], a hydrogen perm-selective reactor was modeled and
studied in 2D. The catalyst considered for the study was Ru/SiO2
which is favorable for steam methane reforming at low tempera-
tures and steam to methane ratios whereas the membrane for
hydrogen permeation was that of palladium. Analysis was made on
the inlet temperature, space velocities, pressures and sweep gas
rate. The inlet temperature and space velocity showed significant
effect on methane conversion among the operating variables
considered. At a space velocity of 8900 h  1, hydrogen permeation
rate was found to be maximum, however to attain a complete
conversion of methane, space velocity of 6000 h  1 was suggested
by the authors.
Coroneo et al. [61] carried out numerical and experimental
investigation of mass transfer performance of Pd–Ag membrane
modules for hydrogen separation. In the analysis, impact of con-
centration polarization and non-ideal flow on design of membrane
separation units was evaluated by using computational fluid
dynamic. In the analysis, the source and sink terms are introduced
on either side of the membrane boundary cell in order to account
for the permeation of hydrogen in the numerical study developed.
The study covered different module configuration for H2 and N2
mixture and compared with the experimental results which were
found to be in good agreement. The analysis extended to the use of
baffles which permits the production of compartments inside the
module, avoiding mixing and increase permeation driving force.
The results show the separation performances of the module
increases with the number of baffles. In all modules, studied the
157
module with baffle resulted in maximum permeates of H2. Shigeo
Goto [70] studied the effect of hydrogen permeation rate through
composite palladium membrane for tubular configuration. A pal-
ladium film was coated on composite membrane tube. The ana-
lysis was done for increasing temperatures for two different
modes. In the first mode, CP mode, H2 was passed through the
tube and pressure was reduced in shell side. Therefore, H2
permeates first ceramic tube and then through the palladium film.
In the second mode, PC mode, H2 was passed from shell side and
pressure inside the membrane tube was reduced and H2 perme-
ates first through palladium film then composite tube. The
numerical models were based on the combined resistances of both
palladium film and composite support. From the results it showed
that with increase of temperature, permeation rate increases
under CP mode. A CFD modeling of inorganic membrane modules
for gas mixture separation was carried out by Coroneo et al. [69].
First, they derived the permeation coefficient, based on the
transport mechanisms for the gas molecules across the membrane.
The basics of molecular diffusion, Knudsen diffusion and viscous
(Poiseulle) flow, and used in the source term formulation in the
continuity and species transport equations. Of all the mechanisms,
the molecular diffusion was dominant on H2 permeation at high
pressures. The mole fraction and permeation rate of hydrogen
increases with increase of working pressure and a good agreement
with the experimental results was found. Staudacher et al. [71]
conducted simulative analysis of mass transfer effects in gas and
vapor permeation modules. The study relates the effect of con-
centration polarization and flow distribution with spacers
between two membrane surfaces. Calculations of permeation as a
function of temperature, pressure and composition were done
using the finite-volume method. The use of baffles in the model
which separates membrane into a number of compartments
helped in velocity control of feed. The flow through the membrane
was implemented as a sink in the basic transport equation for each
finite cell. A user-defined function (UDF) was implemented for the
transport from the membrane using a function for flux propor-
tional to partial pressures. Similar to the work Staudacher et al.
[71], it was found from the results that the driving force obtained
was due to concentration polarization and the use of spacers
which affects the performance of membrane. Iullianelli et al. [72]
studied a dense Pd–Ag membrane reactor packed with a Ni-based
catalyst for the methane steam reforming reaction to be carried
out between reforming temperatures of 400 and 500 °C and
relatively low pressure (1.0–3.0 bar) with the aim of obtaining
higher methane conversion and hydrogen yield than a fixed bed
non-membrane reactor, operating at the same conditions. A 50%
methane conversion was experimentally achieved in the mem-
brane reactor at 450 °C and 3.0 bar whereas, at the same condi-
tions, the fixed bed non-membrane reactor reached a 6% methane
conversion. Moreover, 70% of high-purity hydrogen on total
hydrogen produced was collected with the sweep-gas in the
permeate stream of the membrane reactor. A membrane reactor
consisting of a dense self-supported Pd–Ag tube filled with a Pt-
based catalyst and used for producing pure hydrogen via oxidative
steam reforming of bio-ethanol was studied by Tosti et al. [73].
Capability of the membrane to promote the reaction conversion
due to equilibrium shift effect was demonstrated.
4.2. Coupling membrane reformers to solar parabolic troughs
As we discussed in the previous section, it is possible to over-
come the thermodynamic limitations on CH4 conversion imposed
by low operating temperatures using membrane reformers. Since
in a membrane reformer complete CH4 conversions are achievable
well below 600 °C, such approach is of particular interest for solar
reforming applications since it can be used in conjunction with
158 S.A.M. Said et al. / Renewable and Sustainable Energy Reviews 59 (2016) 149–159
solar parabolic troughs to produce hydrogen. It was recently sug-
gested to use parabolic troughs to provide the heat for methane
steam reforming using indirect approach, with molten salts as heat
transfer and storage medium [74–77]. The indirect solar thermal
reforming approach allows for easy incorporation of solar refor-
mers into the existing parabolic troughs concentrated solar power
plants and the reformer design does not have any special
requirements. In fact, tubular reformer geometry very similar to
industrial reformers can be used.
However, the use of parabolic troughs and molten salts implies
temperature limitations which will be realized in low methane
conversions. Another issue is low activity of Ni-based catalysts at
low temperatures and their tendency to fast oxidation deactiva-
tion. Carbon formation that at low temperatures occurs mainly by
exothermic Boudouard coking and reverse gasification is also a
concern. The use of hydrogen selective membranes to shift the
methane reforming equilibrium towards hydrogen generation is a
promising approach. Selective separation of hydrogen by Pd-based
membranes can allow obtaining nearly complete conversions even
at low temperatures. The price of Pd and the membrane durability
are the main obstacles.
One such scheme of combining solar energy with a membrane
reformer was investigated by Said et al. [78], wherein molten salt
is heated via solar parabolic troughs and sent to the steam
methane membrane reformer. The heat supplied by the molten
salt drives the endothermic reforming reactions for production of
pure hydrogen at the exit of the reactor. In the study performed by
Said et al., low temperature methane reforming in a membrane
reactor heated by a molten salt was analyzed numerically by
computational fluid dynamics over a wide range of operating
parameters. Effects of temperature, steam-to-carbon ratio and
space velocity on conversion, hydrogen recovery and carbon
monoxide selectivity were investigated. The results of numerical
simulations showed that concentration polarization can be sig-
nificant and that the reformer performance can be limited by the
kinetics of the reforming reaction or by hydrogen separation
ability. Nevertheless, the simulations showed that high hydrogen
recovery is achievable even at high, industrially relevant space
velocities.
5. Conclusion
This paper reviews the recent articles that have been published
on solar steam reforming. Steam reforming of methane is one of
the processes for production of hydrogen or synthetic gas, known
for clean combustion and high energy content. Other reforming
processes such as dry reforming, partial oxidation and auto ther-
mal reforming are reported in the literature. These technologies
are currently not suitable for bulk production of hydrogen. Steam
reforming of methane (SMR) which uses Ni based catalyst is an
efficient and cost effective process for the production of hydrogen
and syngas compared with other processes.
The review indicates that the heat requirement for the process
can be fulfilled by solar energy using solar facilities such as solar
parabolic dishes and solar towers. Different steam reforming
reactors configurations are proposed by researchers to efficiently
convert methane into product hydrogen or syngas. These reactors,
mostly tubular, are heated directly or indirectly by solar energy.
Although the solar parabolic troughs are a mature and much
cheaper technology compared to solar towers and dishes, it cannot
be used for steam reforming processes as they do not generate the
required temperature (above 800 °C) for the process. Hence, the
review indicates the development of a reactor suitable for solar
steam reforming using solar parabolic trough technology. These
reactors do perform efficiently with high methane conversions at
low temperatures generated by solar parabolic troughs.
Acknowledgments
The authors highly appreciate and acknowledge the support of
King Fahd University of Petroleum and Minerals through the
research grant # R12-CE-10 offered by KFUPM-MIT Clean Water
and Clean Energy Research Collaboration Center.
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