Journal of Cleaner Production 262 (2020) 121424

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Journal of Cleaner Production

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

Updates on promising thermochemical cycles for clean hydrogen

production using nuclear energy
Rami S. El-Emam a, *, Hasan Ozcan b, Calin Zamfirescu c
a
Faculty of Engineering, Mansoura University, Mansoura, Egypt
b
Faculty of Engineering, Ankara Yildirim Beyazit University, Ankara, Turkey
c
School of Science and Engineering Technology, Durham College, Oshawa, Ontario, Canada

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

Article history: Hydrogen is having a worldwide momentum as a clean versatile energy solution and this is the time for
Received 17 December 2019 nuclear hydrogen production technologies to play its role in securing a clean and affordable energy
Received in revised form future. For over four decades, several nations have been investigating the potential of tens of thermo-
23 March 2020
chemical cycles for efficient and sustainable hydrogen production. These cycles require high quality heat
Accepted 29 March 2020
Available online 2 April 2020
(i.e. heat at high temperatures) solely or along with electric power (i.e. hybrid thermochemical cycles)
both of which can be provided by nuclear energy. This paper delivers a highlight on the potential of
^ as de
Handling Editor: Cecilia Maria Villas Bo nuclear energy for hydrogen production. It also discusses the main features of five of the promising
Almeida thermochemical cycles that are considered for integration with nuclear power plants. Furthermore, the
paper highlights the current status and advances of R&D in these thermochemical cycles as well as cost
Keywords: estimation and the main safety consideration for large-scale nuclear hydrogen production using different
Hydrogen nuclear-driver technologies.
Nuclear © 2020 Elsevier Ltd. All rights reserved.
Economics
Cogeneration
Safety

1. Introduction decision makers and stakeholders towards nuclear hydrogen

In June 2019, the International Energy Agency (IEA) released a
landmark report titled the future of hydrogen: seizing today’s op-
portunities (IEA, 2019a). In the forward of the report executive
summary, Dr. Fatih Birol, Executive Director at the IEA, stated that
“hydrogen is today enjoying unprecedented momentum. The world
should not miss this unique chance to make hydrogen an important
part of our clean and secure energy future”. The report provides
guidance on the future development of hydrogen production and
brings key recommendations for hydrogen production scale up to
stakeholders. This report was preceded by another report from the
IEA on the role of nuclear power in a clean energy system (IEA,
2019b). Since the beginning of the nuclear energy era, it was al-
ways considered as clean and sustainable energy source for inte-
gration with hydrogen technologies for large-scale hydrogen
production. Currently, there is a growing interest supported by
* Corresponding author.
E-mail addresses: rami.elemam@gmail.com (R.S. El-Emam), hozcan@ybu.edu.tr
(H. Ozcan), calin.zamfirescu@durhamcollege.ca (C. Zamfirescu).
production.
During the United Nations Climate Change Conference (COP 25)
held in Madrid, Spain in December 2019, the International Atomic
Energy Agency (IAEA) Director General Rafael M. Grossi stated that
greater use of low-carbon nuclear power is needed to ensure the
global transition to clean energy. He also mentioned that this view
is shared by many of the IAEA’s 171 member states. During the last
quarter of 2019, there was the announcement of three projects at
the USA by three different utility companies to demonstrate
hydrogen production using energy of three nuclear power plants
during 2020 and 2021. These projects are funded by the US
Department of Energy (DoE) with collaboration of several national
laboratories. Another project was announced in UK around the
same time.
Most of currently operating nuclear power plants are of Pres-
surized Water Reactor (PWR) technology where the maximum
temperature does not exceed 350
C (IAEA, 2019). Incorporating
hydrogen production using low-temperature hydrogen technology
(i.e. conventional electrolysis) to operating nuclear power plants of
water-cooled reactor type will improve the competitiveness of
nuclear industry through the cogeneration of hydrogen along with

https://doi.org/10.1016/j.jclepro.2020.121424
0959-6526/© 2020 Elsevier Ltd. All rights reserved.
2 R.S. El-Emam et al. / Journal of Cleaner Production 262 (2020) 121424

electricity. In addition, the use of hydrogen production for energy
storage enables the flexible and load-following operation of these
reactors. This also facilitates the feasible integration of nuclear and
renewable energies in sustainable energy systems.
Many advanced reactors are proposed to increase thermal effi-
ciency of nuclear power plants by increasing the maximum reactor
temperature. Such reactors are feasible to provide the required
source of energy for driving thermochemical hydrogen production
cycles. Fig. 1 gives an idea on the possibilities of nuclear integration
with hydrogen technologies based on the ranges of operating
temperature of the different promising hydrogen technologies and
the quality of the heat provided by the different reactors.
There are several publications in the literature tackling the
development of specific elements in each of the hydrogen ther-
mochemical cycles discussed in the current paper. However, there
is lack of publications gathering the status of progress on these
cycles. This paper highlights the main features and recent advances
of some of the promising thermochemical cycles that possess po-
tential of integration with nuclear power plants for large-scale
hydrogen production. It also discusses the economics of consid-
ering such technologies when available for large-scale production.
technology. Since cycle operating temperature and electrical en-
ergy consumption are two main indicators in the selection of
thermochemical cycles, some selected thermochemical cycles are
comparatively presented in Fig. 2 with respect to these two in-
dicators. However, this figure shows that comparing these cycles
based on their maximum temperature values and electrical energy
consumption may not be solely used to determine the most feasible
option for hydrogen production. One can see the pure thermo-
chemical NaeOeH cycle in which the rate of reaction may not be
feasible at the mentioned maximum temperature. Another pure
thermochemical cycle is the U-Eu-Br cycle whose chemical content
has radioactive components and may bring higher safety and se-
curity concerns. Kinetics study is also inevitable for every individ-
ual reaction in this cycle. The Zn/ZnO cycle has been successfully

2. Thermochemical cycles for hydrogen production

The main motivation behind development of thermochemical

cycles is to reduce the high cost associated with direct electrolysis
of water which is an electric-energy intensive process. Pure ther-
mochemical cycles require heat input at high temperatures for
water splitting process. Thermochemical cycles are seen to reduce
hydrogen generation cost and operate at higher efficiency. How-
ever, high temperature requirements jeopardize the safety of the
process and bring new challenges to the scene such as material
compatibility and operation durations. Therefore, hybrid cycles
have been proposed where electrical energy is utilized along with
thermal energy. This leads to a reduction in the high temperature
requirements and elimination of the associated challenges. In this
paper, the term thermochemical cycle is sometimes used to refer to Fig. 2. Maximum temperatures and theoretical electrical energy requirements of
pure and/or hybrid thermochemical cycles as a general category of selected hydrogen production methods.

Fig. 1. Potential of nuclear reactor technologies for integration with hydrogen production technologies based on ranges of operating temperature.
 R.S. El-Emam et al. / Journal of Cleaner Production 262 (2020) 121424
demonstrated at high temperature using concentrated solar energy
(Steinfeld, 2002) and it requires very high temperature for com-
plete operation. Fig. 2 also shows the two Sulfur-based cycles. The
pure thermochemical SeI cycle has some chemistry complexity and
material compatibilities issues. The chemistry complexity is
reduced in the HyS cycle at the cost of electrical energy con-
sumption. Both cycles have the same range of operating tempera-
tures. The hybrid thermochemical cycles: HyS, CueCl, CaeBr and
MgeCl lie on either side of the diagonal line in Fig. 2, where they
may be noted to be more realistic options. One may comment on
this representation as follows: cycles at the lower side of the di-
agonal line may possess chemistry and reaction rate problems
while the ones at the upper side may possess economic infeasi-
bility. Some recent advances in selected thermochemical cycles are
discussed in next subsections.
2.1. SeI cycles
SeI cycle is the most developed pure thermochemical hydrogen
production cycle that is considered for coupling with nuclear power
plants and expected to operate at relatively high efficiency. The
main merit of this cycle is that all chemicals are in either gas or
liquid form which reduces the power required for transporting
these chemicals (in contrast, most of other cycles require solid
transport). There are several types for the cycle, Fig. 3 presents a
simplified process diagram for the most common SeI cycle
configuration, showing its three reactions: the endothermic
decomposition of H2SO4 (oxygen production process), the
exothermic Bunsen process (hydrolysis step), and the endothermic
decomposition of HI (hydrogen production process); operating at
temperature values 800e850
C, 120
C, and 300e450
C, respec-
tively. However, the heat source needed for SeI cycle is to be at least
at 950
C to count for the heat losses in the heat exchanger. The
reactions of the cycle consume ca. 270e375 kJ of thermal energy
per mole of hydrogen production. In addition, around 50e75 kJ of
electric power per mole of produced hydrogen is required to
operate the auxiliary systems between the different processes of
the cycle.
Several countries have their own national and international
collaborative projects for developing a pilot scale prototype of the
cycle which was first invented in 1970s. One of the initiatives was
the International Nuclear Energy Research Initiative which was
conducted with collaboration between Sandia National
Fig. 3. SeI thermochemical cycle.
3
Laboratories and General Atomics from the United States and the
Atomic Energy Commission (CEA) of France to construct a labora-
tory scale process for the production of 100e200 L of hydrogen per
hour.
The cycle has been considered by the Japan Atomic Energy
Agency (JAEA) for scale-up. Starting with a proof of operation
concept in 1997 by 24 h of operation with 1 L of hydrogen pro-
duction per hour at a laboratory scale test of the process (Nakajima
et al., 1998), and through several solid achievements including one-
week continuous production of 30 L hydrogen per hour using a
bench-scale glass-based test system in 2004 (Kubo et al., 2004),
until the construction and operation of a test facility at JAEA inte-
grating the three sections of the cycle: HI, Bunsen, and H2SO4
sections; and successfully operating it for 8 h with 10 L/h of
hydrogen production in February 2016 (Noguchi et al., 2017), fol-
lowed by successful 31 h of operation with hydrogen production
rate of 20 L/h later in October of the same year. After resolving the
issue of solid precipitation from I2 in the HI decomposition section,
another milestone was achieved, as announced in the JAEA press
release in January 2019, by the continuous operation of the cycle for
150 h with hydrogen production rate of 30 L/h and successful so-
lution circulation in the HI section for three times. Continuous ef-
forts are ongoing to achieve sustainable long-term operation using
industrial materials, and to achieve the coupling with the HTGR
design of JAEA, HTTR (Kubo et al., 2019).
In China, the development of the SeI has progressed nicely since
started with fundamental studies on the cycle in 2005. The Institute
of Nuclear and New Energy Technology (INET) of China has suc-
ceeded in 2009 in conducting a closed-cycle operation of contin-
uous 8 h with the production of 10 L of hydrogen per hour as a
proof-of-concept and proof of the process feasibility. Later in 2013,
a laboratory scale facility, IS-100, was constructed with the aim of
producing 100 L/h, and in 2014 a continuous stable operation of the
system for over 80 h was achieved with 60 h of hydrogen pro-
duction at rate of 60 L/h (Zhang et al., 2018). This was a proof of
cycle controllability and stability, which is followed by continuous
work towards the up-scaling of the process with its coupling to the
HTGR design of HTR-PM600 and HTR-10, and the associated safety
concerns, engineering materials selection, and improving operating
efficiency of the cycle (Zhang et al., 2019).
In addition to several achievements in the Republic of Korea on
the process simulation and the investigation of its static and dy-
namic performance, the Korean Atomic Energy Research Institute
(KAERI) and the Korea Institute of Energy Research (KIER) have
constructed a 50 L/h scale test system to be operated under pres-
surized environment and the start-up dynamic behavior of the
HIeI2eH2O distillation column was studied and reported in the
literature (Shin et al., 2015).
2.2. HyS cycle
The HyS cycle, proposed in mid-1970s, was first developed by
Westinghouse electric corporation (it is also known as the West-
inghouse Cycle) (Brecher and Wu, 1975). An electrochemical step
along with the thermochemical sulfuric acid decomposition step,
hence called hybrid cycle, brings simplification to the cycle
compared to the traditional SeI cycle. This cycle requires around
180 kJ of thermal energy per mole of hydrogen along with
55e80 kJ/mol of electric power.
Further investigation followed in 1970s and 1980s in Westing-
house (Carty et al., 1977; Lu and Ammon, 1982; Lu, 1983). During
the same period, the cycle was studies in Europe, including
research conducted at the European Joint Research Centre and the
German Nuclear Research Centre in Jülich (Struck et al., 1980;
Junginger and Struck, 1982). The HyS comprises two chemical
4 R.S. El-Emam et al. / Journal of Cleaner Production 262 (2020) 121424

reactions: sulfur dioxide depolarized electrolysis of water and

sulfuric acid decomposition. A simplified diagram of the cycle two
steps is shown in Fig. 4.
The thermochemical SO2 depolarized electrolysis of water yields
sufuric acid and hydrogen.

SO2ðaqÞ þ 2H2 OðgÞ /H2 SO4ðaqÞ þ H2ðgÞ at 80  120
C

This process requires one-third of the electric power required

for direct water electrolysis (Dokyia et al., 1977) and this is what
makes HyS process interesting. The SO2 electrolyzer uses the con-
ventional polymer electrolyte membrane (PEM) electrolysis.
However, the depolarization of the anode by SO2 reduces the
standard 1.23 V cell potential. The theoretical potential of this
process is 0.158 V, yet it is targeted to be brought down to less than
half of this value at 500 mA/cm2. This process actually occurs in two
main steps. First, the electrochemical oxidization of SO2 at the
anode forming sulfuric acid, protons and electrons.

SO2ðaqÞ þ 2H2 OðgÞ /H2 SO4ðaqÞ þ 2Hþ þ 2e

The protons are then conducted through the electrolyte sepa-

rator to the cathode side to form hydrogen with the electrons.

2Hþ þ 2e /H2ðgÞ

Different designs of the SO2-depolarized electrolysis were

developed after the initial design of Westinghouse. Fig. 5 shows
two schematics of different SO2-depolatized PEM electrolysis
designs.
The endothermic thermochemical reaction of sulfuric acid
decomposition requires heat at temperature of at least 750
C.

H2 SO4ðaqÞ / SO2ðgÞ þ H2 OðgÞ þ 0:5O2ðgÞ at 800
C

This thermochemical reaction step of the HyS cycle is similar to

the one occurring at the SeI process and is common in all other
sulfur cycles. Sulfuric acid is dehydrated through heating and
eventually sulfur dioxide is formed and then it thermally de-
composes. The decomposition of sulfuric acid into SO3 and vapor
Fig. 5. Schematic of SO2 depolarized PEM electrolysis cell with water fed at the
occurs first at around 800
C or more as bellow: cathode and the anode is fed with: (a) SO2 dissolved in sulfuric acid and (b) gaseous
SO2.
H2 SO4ðaqÞ / SO3 þ H2 OðgÞ

This is followed by the catalytic decomposition of the resulted

SO3 producing sulfur dioxide and oxygen. This part of the decom-
position is processed at lower temperature, yet higher than 450
C.
Fig. 4. HyS hybrid thermochemical cycle.
SO3 / SO2ðgÞ þ 0:5O2ðgÞ
Different alternatives of the cycle were investigated in several
countries, including: USA, France, Japan, and Canada, to reach a
configuration with lower maximum temperature for the endo-
thermic reaction, considering heat source of 500e700
C. Other
projects were also conducted in the Republic of Korea and South
Africa. Along with the SO2 transportation through the electrolyzer
membrane and the sulfur buildup at certain parts of the cycle,
finding the proper catalyst for the electrolysis to proceed is one of
the main challenges for this cycle.
On a related topic, the use of sulfur based thermochemical en-
ergy storage is considered by the ongoing PEGASUS project funded
by Horizon 2020 European Union programme. Concentrated solar
thermal energy is utilized for the decomposition of sulfuric acid
where the produced sulfur dioxide is decomposed in a dispropor-
tionation reaction to elemental sulfur and sulfuric acid. Sulfur is
later combusted in air producing high quality heat of over 1000
C.
Even though this is not a hydrogen production route, yet the
development of this part of the cycle at industrial large-scale level
would help enabling sulfur-based thermochemical cycle. Anyway,
the decomposition of sulfuric acid has been already investigated in
 R.S. El-Emam et al. / Journal of Cleaner Production 262 (2020) 121424
the literature. In general, the HyS cycle faces some challenges
including the optimization of the electrochemical step of the cycle
(i.e. sulfur dioxide depolarization of electrolysis) reducing the
process overpotential. Another technical challenge in this step is
sulfur dioxide transport through the membrane. The catalysts ac-
tivity and degradation in the electrolyzer is another challenge that
has been widely investigated in the literature and still under
development (Diaz-Abad et al., 2019), along with the investigation
on high-corrosion resistive materials for the cycle processes in
general. The cycle should be avoided to operate below 120
C to
avoid sulfur buildup in the cycle components as this is the nominal
melting point of sulfur.
2.3. CueCl cycle
Various configurations of the hybrid copper-chlorine cycle were
proposed starting with the work of Dokyia and Kotera (1976) and
the US Institute of Gas Technology as reported in Carty et al. (1981).
In one main variant, the electrochemical process of this hybrid cycle
generates copper from CuCl oxidation. This variant is known as the
five-step CueCl hybrid thermochemical cycle and its main pro-
cesses are shown in Fig. 6. Hydrogen is generated in a thermo-
chemical reaction of chlorination, and oxygen is produced by a
thermolysis process.
Starting with the work published in Naterer et al. (2010) a more
appealing four step version of the copper-chlorine cycle, which
includes a hydrogen-generating electrochemical step is in devel-
opment. The four-step cycle is based on two thermochemical pro-
cesses, one electrochemical step and a separation process. In
Naterer et al. (2010) the separation process in based on CuCl2
crystallization in an aqueous solution, but in other developments a
drying process is used to extract salts from the electrolyte oxidized
in the electrochemical cell. In Naterer and Wang (2016) a drier-
based four-step copper-chlorine thermochemical water splitting
cycle is disclosed.
Zamfirescu et al. (2017) recognizes the fundamental role of the
anodic electrolyte e also known as anolyte e in chemical transport,
separations, and chemical conversions within the cycle. In a
reduced form, the anolyte consists of CuCl dissolved in strong
HCl(aq) and is feed at the electrochemical process. In the oxidized
form, anolyte consists of CuCl and CuCl2 dissolved in strong HCl(aq)
as it is generated in the electrochemical unit. Fig. 7 shows how
anolyte bridges between electrochemical and thermochemical
processes of the cycle. As shown in El-Emam et al. (2019), the cycle
requires ca. 200 kJ per mole of H2 to run its thermochemical pro-
cesses, which split water molecule and generate oxygen gas, while
in the same time reduce the anolyte which has been oxidized in the
Fig. 6. Five-Step CueCl hybrid thermochemical cycle.
5
Fig. 7. Hybrid thermochemical CueCl cycle with hydrogen evolving electrochemical
step.
electrochemical unit. Hydrogen evolves separately, at the cathodic
circuit of the electrochemical cell which include a membrane for
separation of anolyte from catholyte (cathodic electrolyte). Cath-
olyte typically consists of a strong solution of HCl(aq).
From Zamfirescu et al. (2017) a flow sheet of CueCl cycle con-
sisting of three reaction steps and one separation step is shown in
Fig. 8. The separation step is complex. It is driven thermochemi-
cally, and also involves pumps, stirrers and conveyors. The sepa-
ration process involves drying with recycling of strong HCl(aq)
though subsequent condensation. Drying produces a mixed salt
consisting of CuCl and CuCl2. Subsequent separation of salts is
conducted to a selective dissolution of CuCl2 in water, as CuCl re-
mains insoluble and can be extracted from sediment or by filtration.
On additional separation aspect relates to the making-up of HCl to
the required concentration for the reduced anolyte. In electro-
chemical unit HCl is consumed. To make up the HCl, the output of
the hydrolysis unit is used, which generates HCl. Nevertheless, no
pure HCl is obtained anywhere within the cycle. HCl is present
either as mixed vapor with steam or as aqueous solution. Water
must be then removed from the oxidized anolyte, while in the same
time strong HCl(aq) is added to re-make the reduced anolyte. A
pressure swing distillation unit to concentrate HCl(aq) and recycle
water is therefore one recommended choice. This unit can be
operated on thermal energy at max. 200
C. Making-up the anolyte
also requires addition of CuCl from thermolysis, which yield as
molten salt, but is further quenched in water and separated as
dense sediment. The reduced anolyte is produced in the dissolution
cell of recycled and newly generated CuCl; where the salt dissolved
in strong HCl(aq). A detailed flowsheet of the four-step cycle pre-
viously discussed is due to Farsi et al. (2019) .
2.4. MgeCl cycle
MgeCl cycle is a configuration of the Reverse Deacon cycle in
which HCl electrolysis for H2 and Cl2 production occurs. Here HCl
production is accomplished with subsequent reactions of MGCl2 hy-
drolysis and MgO chlorination (Simpson et al., 2006). The three-step
cycle has potential problems of having high maximum temperature
and intense heat requirement for hydrolysis while the pore size of the
produced MgO particles do not allow chlorination at higher reaction
rates (Ng et al., 2005; Kashani-Nejad et al., 2005). Therefore, an
additional step is developed based on the two known three-step
configurations of this cycle to decrease cycle thermal and electrical
energy requirements (Ozcan and Dincer, 2016a, Ozcan and Dincer,
2018a,b). The four-step cycle shown in Fig. 9 considers an interme-
diate exothermic reaction for MGCl2 hydrolysis and then decomposes
6 R.S. El-Emam et al. / Journal of Cleaner Production 262 (2020) 121424
Fig. 8. Flowsheet of a four-step CueCl water splitting cycle, based on Zamfirescu et al. (2017).
Fig. 9. MgeCl hybrid thermochemical cycle.
the product (MgOHCl) for dry HCl production at 450
C. This config-
uration solves two main problems of the MgeCl cycle. First, MgO
produced from MgOHCl decomposition has higher reactivity with the
chlorine gas and second, dry HCl electrolysis requires lower electrical
energy consumption. Comparative thermal analysis and integration
of the four-step cycle can be found elsewhere (Ozcan and Dincer,
2016b; Ozcan and Dincer, 2016c). Mature chemical reactions and
electrolysis step, and favorable reaction rates makes the cycle a
feasible one for further consideration (Ozcan, 2015). The cycle theo-
retically consumes around 151.5 kJ of thermal energy and 190 kJ of
electric power per mole of produced hydrogen with theoretical cell
potential of 0.99 V.
2.5. CaeBr cycle
A four-step cycle has first been proposed and analyzed as a pure
thermochemical form called the UT-3 cycle, where hydrogen pro-
duction step requires use of iron-oxides (Nakayama et al., 1984).
The UT-3 cycle uses iron bromide and iron oxide intermediates for
recycling the reagents and for hydrogen evolving in two reaction
steps (Yoshida et al., 1990; Sakurai et al., 1996b; Simpson et al.,
2007; Teo et al., 2005). The UT-3 reactions are as follows:
CaBr2ðsÞ þ H2 OðgÞ /CaOðsÞ þ 2HBrðgÞ at 700  750
C
3FeBr2ðsÞ þ 4H2 OðgÞ /Fe3 O4ðsÞ þ 6HBrðgÞ þ H2ðgÞ at 550


 600 C
Fe3 O4ðsÞ þ 8HBrðgÞ /3FeBr2ðsÞ þ Br2ðgÞ þ 4H2 OðgÞ at 200


 300 C
CaOðsÞ þ Br2ðgÞ /0:5O2ðgÞ þ CaBr2ðsÞ at 500  600
C
In this cycle, solid reactants are used cyclically in heterogeneous
reactors. The reaction rate of CaBr2 hydrolysis reaction is the
slowest, which limits the rates of other reactions. A hybrid version
of the UT-3 cycle was proposed, using a single electrochemical re-
action of dissociation of hydrobromic acid at 50
C, which evolves
hydrogen and regenerates bromine.
The hybrid CaeBr cycle is a modified version of the UT-3 cycle
which includes four-reaction steps with heat requirements at
around 750
C and up to 800
C (Doctor et al., 2004; Lottes et al.,
2009; Aihara et al., 1990; Sakurai et al., 1996a). This hybrid imple-
mentation of the CaeBr in an electro-thermochemical cycle con-
siders two thermochemical reaction in addition to HBr electrolysis
 R.S. El-Emam et al. / Journal of Cleaner Production 262 (2020) 121424
occurring at temperature not more than 100
C. These are two gas-
solid reactions and one gas phase reaction:
CaBr2ðsÞ þ H2 OðgÞ /CaOðsÞ þ 2HBrðgÞ at 750
C
CaOðsÞ þ Br2ðgÞ /0:5O2ðgÞ þ CaBr2ðsÞ at 580
C
2HBrðgÞ / Br2ðgÞ þ H2ðgÞ at 100
C
The decomposition of HBr through electrolysis in this cycle
replaced the other versions using thermal decomposition and
plasma reaction. However, the main challenge in this configuration
was due to the low solubility of CaO in CaBr2 and deposition of CaO
at the reactor inlet (Simpson et al., 2007). This three-step cycle
phases out the use of iron-oxide and directly electrolyzes CaeBr
agent from the hydrolysis step which makes the cycle simpler.
However, electricity is required to drive the process. The four-step
cycle efficiency is as high as 50% while the hybrid three-step cycle
may possess around 47% energy efficiency with the electrolysis
process that requires less than half of the electrical energy required
for conventional water electrolysis (Sakurai et al., 1996b). The
maximum cycle temperature makes this hybrid cycle compatible
for coupling with advanced nuclear reactors. Even though many
previous studies have been conducted for the pure CaeBr cycle, not
many detailed studies are present for the hybrid version. Fig. 10
shows a schematic of the hybrid version of the cycle.
2.6. Other promising cycles
Even though experimental results show reasonable reaction
kinetics for the two-step pure Zn/Zno and Cr/CrO thermochemical
cycles, very high temperature requirements make these configu-
rations only compatible with concentrated solar energy systems.
The U-Eu-Br heavy-element halide cycle has been proposed as a
pure thermochemical cycle that can even match with the existing
nuclear reactors that has a maximum temperature of 310
C only,
makes this cycle to be the lowest temperature requiring pure
thermochemical cycle (Petri et al., 2007). The proof-of-concept
reactions show proceed in reactions in very small experimenta-
tion. Further studies are required for reactor integration, thermal
analysis and reaction kinetics, as well as for safety. Hydrogen from
low temperature sodium redox reactions is first proposed to be
accomplished at 400
C (Miyaoka et al., 2012). Individual reactions
are designed as cyclic processes to represent their feasibility. Even
though the cycle represents low maximum temperatures, further
Fig. 10. CaeBr hybrid thermochemical cycle.
7
research is required for the reaction kinetics which may lead to
increased maximum cycle temperatures. It is depicted that the
maximum cycle temperature is achievable at around 500
C at
vacuum pressure conditions which in general accepted as a chal-
lenging process as depicted in previous studies for other promising
cycles (Marques et al., 2018). An exergy analysis for the cycle was
found as 83% while practical aspects are not included such as excess
water ratio (Marques et al., 2020).
3. Economics, environmental and safety aspects
As discussed, due to its abundance, steadiness, and trans-
portability, nuclear energy is a feasible option for clean and cost-
effective hydrogen production. However, many aspects need to be
taken into account starting from economics to stakeholders. Clean
hydrogen production using conventional electrolysis might be the
most cost-effective route when the driving electricity is generated
from nuclear or geothermal energy systems (El-Emam and Ozcan,
2019). Even though thermochemical cycles are designed for the
production of low-cost hydrogen efficiently, the need for high
temperature and material compatibility issues bring high cost
associated with technology and safety needs. Fig. 11 represents cost
ranges of nuclear hydrogen generation using different hydrogen
production technologies. It should be noted that the variations in
the costs are dependent on capacity, size, and other specific plant
configuration. In the figure, one can see that HyS brings a wide
range of hydrogen production cost variation compared to other
technologies since many studies are present for stoichiometric and
lab scale studies. Reported cost for the CueCl and MgeCl cycles are
among the lowest when considering stoichiometric conditions
while high limits of their cost ranges are for more practical sce-
narios. Under realistic conditions, the ratio of steam for hydrolysis
is very large and this requires larger components and reactors for
the cyclic process to complete, hence, higher plant investment
costs. HTSE is of relatively lower cost compared to thermochemical
cycles as it does not require large reactors nor controlled cyclic
processes. The highest cost contributor for the HTSE cycle is the fuel
cost (i.e. cost of electric power) even though the electricity con-
sumption is over 20% less than that of low temperature electrolysis.
There are several tools used for hydrogen cost estimation such as
Generation IV Excel Calculations on Nuclear Systems (G4ECONS)
and Hydrogen Economy Evaluation Program (HEEP), mainly using
nuclear energy (Sadhankar et al., 2018; El-Emam et al., 2015; Ozcan
et al., 2014; El-Emam and Khamis, 2017, 2019). US Department of
Energy (DOE) targets the centralized hydrogen cost from electrol-
ysis to be $2/kg by 2020. This target probably requires govern-
mental promotions to encourage investment.
With regards to environmental aspects, two of the indicators for
environmental impact assessment are considered here: Global
Fig. 11. Cost of hydrogen produced using nuclear energy driven technologies (Modified
from El-Emam and Ozcan, 2019).
8 R.S. El-Emam et al. / Journal of Cleaner Production 262 (2020) 121424
Warming Potential (GWPeCO2eq) and Acidification Potential
(APeSO2eq). Fuel mining, preparation, transportation and use
include a major amount of total emissions from a nuclear plant.
Even though there are also emissions due to construction and
operation of nuclear plants, their environmental impacts are
significantly lower than conventional fossil-driven power plants
that makes nuclear source a clean and sustainable one. Hydrogen
generation plant is also of importance when it comes to environ-
mental impact. Requirement for noble materials and use of mate-
rials of finite nature in electrolysis processes have impact on the
environment. Hybrid and pure thermochemical cycles have lower
environmental impact than that of nuclear driven HTSE and PEM
plants (El-Emam and Ozcan, 2019). Nuclear driven hydrogen pro-
duction is one most environmentally benign options for clean
hydrogen generation that shows promising values with hydro- and
wind-driven hydrogen technologies, and significantly lower than
those of biomass gasification and Photovoltaic based
configurations.
When it comes to safety aspects, hydrogen carry a large range of
flammability which makes it risky compared to other explosives
even though it has lower flammability limit than many other
combustibles (Fischer, 1986). However, this does not provide any
advantage over other combustibles since ignition sources with the
lower limit is always present. Hydrogen also has higher burning
velocity and similar flame temperature with compared gases.
Deflagration related overpressures of hydrogen-air mixture under
stoichiometric conditions are at a maximum of 8:1 while it doubles
when the detonation occurs in closed containments such as pipe-
lines, which is the leading cause for deflagration-to-detonation
transition (DDT) (Crowl, 1992). The theoretical energy content of
hydrogen is 24 times higher than the same mass of TNT, which
provides a theoretical upper limit for explosion energy. However,
low energy density of hydrogen decreases this value to 2, under
atmospheric conditions. Some experimental results suggested that
only 10% of the theoretical energy is released because only small
amount of released hydrogen is at flammability range (Crowl, 1992,
Jeremi c and Baji
c, 2006). Correlation of survivability after being
exposed to overpressures due to explosion has been conducted by
Gibson (1994) that provides an adequate insight on possible effect
of hydrogen explosion on people. Various sizes of TNT explosives
are considered for the correlations. Specified effect of a blast on
people and structures are based on phase duration of an explosive
and overpressure related shock waves (Tolias et al., 2018).
Studies on hydrogen safety has increased after feasible tech-
nologies are demonstrated. A report based on experiments
demonstrated that hydrogen can be safer than other gaseous
combustibles based on its low energy density and fast dissipation
while less safe due to its tendency to detonate and wide flamma-
bility range (Cracknell et al., 2002). Review of many hydrogen ex-
plosion accidents in the world provide suggestions for safer
hydrogen generation by depicting on advanced ventilation in
congested areas (Ng and Lee, 2008). Rodionov et al. (2011) evalu-
ated risks of hydrogen use in mobile applications and they resulted
that added risk of hydrogen use is only 0.2% which is a residual
contribution. Verfondern et al. (2017) determined safe distances of
hydrogen plants from the nuclear reactor when nuclear based
hydrogen generation is considered. Risks of toxic leakages from the
Sulfur-Iodine hydrogen plant are also reported. More information is
available at El-Emam and Dincer (2018).
4. Conclusion
Today, hydrogen is widely used in several industries including
the production of fertilizers and in oil refineries. This is expected to
expand much more in the near future for serving new sectors and
larger markets of energy storage, transportation and power gen-
eration. Nuclear energy is one of the main alternatives to cope with
the thermal and electrical energy demand for the promising
hydrogen production technologies considered for large-scale pro-
duction of low/zero-carbon hydrogen. Some of the pure and hybrid
thermochemical technologies are among the promising technolo-
gies considered for nuclear hydrogen production.
The SeI cycle shows good potential for large-scale hydrogen
production at competitive cost and high efficiency. However, it
faces some chemical kinetics and solution thermodynamics un-
certainties that were discussed in the literature and are still being
investigated. Among the challenges facing this cycle are the
worldwide availability of iodine for supporting large-scale sus-
tainable hydrogen production and the near-term availability of
economic and clean sustainable heat source. With regards to the
HyS cycle, the main elements requiring further development to
reach commercial scale include: improving electrocatalysts to
reduce the cell potential of the SO2 depolarized water electrolysis,
resolving the problem of SO2 crossover during the process, and
long-term stable operation at low operating potential degradation.
The target operating condition of the electrolysis process of the HyS
cycle is around 0.6 V per cell at around 120
C or less. This gives
potential to bring electricity consumption to one quarter that of
direct water electrolysis. The CueCl cycle has seen recent progress
in the development on integrated laboratory scale demonstration.
Further steps towards a pilot plant would be necessary before this
cycle can take a solid step towards commercialization. Other cycles,
including MgeCl and CaeBr cycles have been seeing slow progress
and some are still facing large amount of uncertainties and chal-
lenges with regards to the chemical kinetics, thermodynamics of
involved solutions, and chemistry of occurring side reactions.
In general, the availability of low-carbon cost-effective heat
source at the necessary quality (i.e. temperature) required for the
corresponding hydrogen thermochemical cycle is possible consid-
ering the advanced nuclear reactor designs. However, the current
fleet of nuclear power plants as well as those under construction
still do not meet the requirements to be coupled with medium/high
temperature thermochemical cycles of hydrogen production. The
consideration of heat-quality upgrade may facilitate such
integration.
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