Nuclear Engineering and Design 233 (2004) 355–362

A pilot test plan of the thermochemical water-splitting

iodine–sulfur process
Shinji Kubo∗ , Seiji Kasahara, Hiroyuki Okuda, Atsuhiko Terada, Nobuyuki Tanaka,
Yoshitomo Inaba, Hirofumi Ohashi, Yoshiyuki Inagaki, Kaoru Onuki, Ryutaro Hino
Department of Advanced Nuclear Heat Technology, Japan Atomic Energy Research Institute, 3607 Niihori, Narita-cho,
Oarai-machi, Higashiibaraki-gun, Ibaraki 311-1394, Japan

Received 20 January 2004; received in revised form 27 April 2004; accepted 9 August 2004

Abstract

Research and development (R&D) of hydrogen production systems using high-temperature gas-cooled reactors (HTGR)
are being conducted by the Japan Atomic Research Institute (JAERI). To develop the systems, superior hydrogen production
methods are essential. The thermochemical hydrogen production cycle, the IS (iodine–sulfur) process, is a prospective candidate,
in which heat supplied by HTGR can be consumed for the thermal driving load. With this attractive feature, JAERI will conduct
pilot-scale tests, aiming to establish technical bases for practical plant designs using HTGR. The hydrogen will be produced at
a maximum rate of 30 m3 /h, continuously using high-temperature helium gas supplied by a helium gas loop, with an electric
heater of about 400 kW. The plant will employ an advanced hydroiodic acid-processing device for efficient hydrogen production,
and the usefulness of the device was confirmed from mass and heat balance analysis. Through design works and the hydrogen
production tests, valuable data for construction and operation will be acquired to evaluate detailed process performance for
practical systems. After completing the pilot-scale tests, JAERI will move onto the next R&D step, which will be demonstrations
of the IS process to which heat is supplied from a high-temperature engineering test reactor (HTTR).
© 2004 Elsevier B.V. All rights reserved.

1. Introduction velop a hydrogen energy system, for which huge hy-

Hydrogen has ideal characteristics as an energy car-
rier. Therefore, the concept of a hydrogen energy sys-
tem has attracted worldwide interest. In order to de-
∗ Corresponding author. Tel.: +81 29 282 8739;
fax.: +81 29 282 8741.
E-mail address: kubo@popsvr.tokai.jaeri.go.jp (S. Kubo).
drogen demand is expected, the development of an ef-
ficient hydrogen production system is an urgent issue.
Nuclear energy that emits no CO2 and that can sta-
blely supply a huge amount of energy is a promising
candidate for the primary energy for massive hydrogen
production. As for the nuclear energy as the source,
the high-temperature gas-cooled reactors (HTGR) that
features a high level of inherent safety and that can

0029-5493/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.nucengdes.2004.08.018
356 S. Kubo et al. / Nuclear Engineering and Design 233 (2004) 355–362

supply heat of ca. 1000 ◦ C is suitable for this purpose.

As for hydrogen production, thermochemical water-
splitting processes are the methods that effectively use
very high temperatures.
The IS process (or the SI process) that uses iodine
and sulfur is a variation of the thermochemical process
proposed and studied by the General Atomic Co. The
process has the attractive feature of consuming nuclear
energy so that an endothermic reaction takes place with
large heat absorption in temperature to be given out by
HTGR. The potential of the IS process for large-scale
hydrogen production has been indicated by prelimi-
nary process flow sheet analysis reported from several
researchers (Norman et al., 1982; Knoche et al., 1984;
Roth and Knoche, 1989; Oeztuerk et al., 1989). Stud- Fig. 1. Reaction scheme of the IS process.
ies including experimental works on the IS process are
currently being conducted in USA and France. SNL
into upper and lower solutions with a clear boundary.
and GA in USA and CEA in France are collaborating
The separated hydriodic acid dissolves the iodine and
in tests on the unit reaction sections with a test scale of
is denoted as the HIx phase. After purification, hydri-
100 L-H2 /h, under prototypical conditions. Loop op-
odic acid is separated from iodine by distillation. The
eration by combining unit reactions after FY2005 is
HI is then decomposed to produce hydrogen (2). Sim-
planned.
ilarly, the separated sulfuric acid denoted as the sul-
The Japan Atomic Research Institute (JAERI) has
furic acid phase is purified, concentrated, vaporized
also conducted tests to develop the IS process. This
and decomposed to produce oxygen. Here, the decom-
paper describes the pilot-scale test that JAERI plans
position reaction (3) proceeds endothermically in two
to implement in R&D driving for industrializing, and
stages: firstly, the sulfuric acid decomposes sponta-
outlines the pilot-scale test plant including brief spec-
neously into sulfur trioxide and gaseous water at ca.
ifications as well as mass and heat balance.
400 ◦ C, and secondly, at higher temperatures, the sulfur
trioxide decomposes into sulfur dioxide and oxygen in
the presence of a solid catalyst. Thus, these three reac-
2. Reaction scheme of IS process tions make a chemical cycle that is an energy converter
from heat to hydrogen.
A scheme of the IS process is shown in Fig. 1. The The upper values of the thermal efficiencies in
process is composed of the following chemical reac- the conversion are estimated from exergy analysis
tions:

I2 + SO2 + 2H2 O → 2HI + H2 SO4 (1)

2HI → H2 + I2 (2)

H2 SO4 → SO2 + 0.5O2 + H2 O (3)

The so-called Bunsen reaction (1) is an exothermic

sulfur dioxide gas-absorbing reaction in an aqueous
phase. The hydriodic acid and the sulfuric acid formed
are separated by a liquid–liquid phase separation phe-
nomenon that occurs in the presence of an excess of
iodine. Fig. 2 shows the liquid–liquid phase separation
phenomenon in a glass vessel. The two acids divide Fig. 2. Liquid–liquid phase separation phenomenon in a glass vessel.
 S. Kubo et al. / Nuclear Engineering and Design 233 (2004) 355–362
Fig. 3. Diagram of energy conversion from heat to hydrogen of 1 mol.
(Nomura et al., 2003). Fig. 3 shows a diagram of energy
conversion from heat to hydrogen of 1 mol. In this fig-
ure, the energy form transforms from left to right. The
axis of the ordinate indicates exergy ratio ε, which rep-
resents the ratio of available energy to enthalpy change.
E
ε= , (4)
H − H0
where E is the energy at a certain state, H is the enthalpy
at a certain state, and H0 is the enthalpy at the standard
state (25 ◦ C, 1 atm). Primarily, a temperature of 950 ◦ C
Fig. 4. R&D stage for the IS process at JAERI.
357
has an energy of 237 kJ through an enthalpy change of
435 kJ as its ␧ is 0.545. The heat converts to hydrogen
whose exergy is 237 kJ, provided that the exergy is not
lost. Since ε of hydrogen is 0.83, its enthalpy is 286 kJ,
the higher heat value of hydrogen per 1 mol remains,
while the remaining heat is rejected into the environ-
ment in the standard state. The thermal efficiency of
the conversion process is given by,
HHHV
η= , (5)
Hheat
where HHHV is the higher heat value of hydrogen, and
Hheat is the enthalpy of the heat. In this case, η is eval-
uated as 0.657.
3. Characterization of pilot-scale test in R&D
for the IS process
3.1. Purpose of pilot-scale tests
Our R&D goal is the industrializing the hydrogen
production system using the IS process with HTGR.
To achieve this, JAERI has been striving to develop
the process for many years. Fig. 4 shows R&D stage
358 S. Kubo et al. / Nuclear Engineering and Design 233 (2004) 355–362
of the process. We are currently at the bench-scale
stage, and hereafter, demonstrations of the IS process
to which heat is supplied from a high-temperature en-
gineering test reactor (HTTR-IS process test) are es-
sential. HTTR, a graphite-moderated and helium-gas-
cooled reactor with a thermal power of 30 MW, has
been constructed by JAERI, and is undergoing safety
demonstration tests and rise-to-power tests to achieve
an outlet gas temperature of 950 ◦ C. In the preliminary
step toward the demonstrations, we are planning a pilot-
scale test that includes construction and operation.
Through the design for the pilot-scale plant, the
main specifications and data requirements for the con-
struction of the HTTR-IS process test plant will be de-
clared. In addition, the codes needed for the design
works will be developed, and they will be verified in
the pilot tests. Moreover, through fabrications and tests,
the following are expected: prospects for materials that
resist corrosive environments, certainty of the mechan-
ics of the equipment, control methods for the process
related to the reactor as a heat source, precise estimation
of thermal efficiency and construction costs, advanced
designs in thermal efficiency, and rationalization of the
system for economy.
3.2. Subjects for current R&D
JAERI carried out fundamental studies on the IS pro-
cess at the lab-scale stage, after which bench-scale stud-
ies have been conducted up to now. The bench-scale
studies cover three fields including advanced HI pro-
cessing, the bench-scale demonstration for hydrogen
production and the screening of corrosion-resistant ma-
terials. They are scheduled for completion in Japanese
FY2004, and we are on schedule with our R&D. Later
on, after completing the current R&D, we will move
onto a pilot-scale test as the next R&D step. The re-
sults and technical knowledge obtained from the cur-
rent R&D will be incorporated into the pilot-scale plant.
Brief descriptions of each of the current R&D areas,
which are basic technologies to progress to the next
R&D stage, are as follows:
(1) Improvement in the processing method of the HIx
solution and evaluation of thermal efficiency have
been conducted (Onuki et al., 2001; Hwang et al.,
2003; Kasahara et al., 2003). In beaker-scale ex-
periments, we found that the concentration of the
HIx solution using an electrodialysis device was
of an over-quasi-azeotropic composition that sep-
arated pure HI from the HIx solution. There are
prospects for the improvement of the thermal ef-
ficiency to adapt these technologies. Theoretical
studies on the evaluation and optimization of ther-
mal efficiency of the process system are also on
going.
(2) Demonstration of continuous and closed-cycle op-
eration using glass apparatus (Kubo et al., 2001) to
confirm controllability and operating procedures
was carried out; this apparatus can produce 50 L/h
of hydrogen. We accomplished 20 h of operation
using the apparatus. H2 production was almost sta-
ble at a rate of 31.5 L/h, and the production ratio
of oxygen to hydrogen almost agreed to 0.5:1.
(3) For the selection of structural engineering materi-
als (Imai et al., 1982; Onuki et al., 1993, 1994),
to fabricate large-scale, high-pressure equipment,
and the conception of key equipment such as heat-
exchanging-type reactors, we found the candidate
materials showing corrosion resistance in typical-
process environments through a number of corro-
sion tests.
4. Outline of the pilot-scale test plant
4.1. Brief specifications of the pilot-scale plant
Fig. 5 shows a simplified flow sheet of the pilot plant,
which is currently tentative. We will begin producing
conceptual designs, flow sheets, basic engineering, trial
manufacture and simulation codes for the pilot-scale
plant from the beginning of Japanese FY2005. After ac-
complishing detailed design, construction of the pilot-
scale plant will start at the beginning of FY2006. The
plant will operate after FY2008.
Our provisional specifications are listed below. The
ability to produce hydrogen will be 30 N m3 /h, and the
maximum operating pressure and temperature will be
4 MPa and 880 ◦ C, respectively. The plant will be as-
sembled using practical materials, heat-resistant met-
als, ceramics, materials for coating/lining and so forth,
for industrial use. A high-temperature helium gas to
drive the process will be provided for the plant. The he-
lium gas loop with an electric heater of about 400 kW
will be employed to supply the helium gas. Thus, the
 S. Kubo et al. / Nuclear Engineering and Design 233 (2004) 355–362
Fig. 5. Simplified flow sheet of the pilot-scale plant.
reactors, which require high temperature, will have to
be of the heat-exchanging type. The electrodialysis de-
vices that JAERI has been studying to concentrate the
molar fraction of the HIx solution will be applied to
improve thermal efficiency.
To clarify the usefulness of applying the electrodial-
ysis devices, the mass and heat balance were compared
between a conventional case and an advanced case.
4.2. Mass and heat balance of conventional flow
sheet
Fig. 6 shows the mass and heat balance of the con-
ventional case, the simplest flow sheet for the IS pro-
cess, to gain hydrogen of 1 mol. The flow sheet of this
figure and the flow sheet of Fig. 1 are almost the same.
The enthalpy-changes with the state-changes and the
rough standard of temperatures are shown. As for heat
balance, the enthalpies at a certain state are calculated
from the thermodynamic data (Chase, 1998; Nihonk-
agakukai, 1993). For the enthalpy-changes calculated
from the difference in enthalpies, reaction heat, latent
heat, sensible heat, mixing heat and separating heat are
counted except for the dilution enthalpies of I2 solu-
tions, and the effects of pressure are not considered.
As for the mass flow, the number of moles has been
simplified, and following assumptions are adopted for
principle conditions. The reacted mixture of the Bunsen
reaction is separated into solutions of molar ratios of
359
about H2 SO4 :H2 O = 1:4 and HI:I2 :H2 O = 1:4:5 (flow
no. 1, Norman et al., 1982). The sulfuric acid is con-
centrated up to about 90 wt.% (flow no. 2), gaseous
H2 SO4 is decomposed into SO3 and H2 O without ex-
ception (flow no. 3), SO3 is decomposed into SO2 and
O2 with a conversion ratio of about 83%, and the unde-
composed residues are recycled (flow no. 4). Regard-
ing the hydriodic acid, azeotropes composed of HI and
H2 O whose molar ratio of 1:5 is separated from the
HIx solution (flow no. 5), gaseous HI is decomposed
with a conversion ratio of about 20% (flow no. 6), and
undecomposed residues are recycled (flow no. 7). The
required and the removed heat to drive the process are
given in Table 1.
The whole enthalpy changes in the figure were
added, and HHHV per 1 mol of 286 kJ is obtained. In ad-
dition, a large amount of materials unrelated to the pro-
duction of hydrogen are recycled through the process,
and huge thermal loads are found in the HIx processing.
If Hheat in Eq. (5) is placed on sum of the required heat,
η is estimated as 6.4%. Waste heat recovery, reduction
Table 1
Required and the removed heat to drive the process
Required heat (kJ) Removed heat (kJ)
H2 SO4 processing 757.2 −472.6
HI processing 3663.2 −3553.1
Others 27 −135.7
360 S. Kubo et al. / Nuclear Engineering and Design 233 (2004) 355–362

Fig. 6. Mass and heat balance of the simplest flow sheet.

in recycling amount and optimization of the total sys-

tem are essential to improve thermal efficiency.

4.3. Mass and heat balance applying an

electrodialysis device

There have been several proposals on the process-

ing scheme for the HIx solution. On the separation
of HI from the HIx solution, an extractive distillation
(Norman et al., 1982) and a reactive distillation (Roth
and Knoche, 1989) have been proposed. In addition,
operation in the liquid phase that uses homogeneous or
heterogeneous catalysts (Norman et al., 1982), has been
proposed for HI decomposition. JAERI has proposed
a preconcentration method using a membrane technol-
ogy, electrodialysis. A view of advanced HI processing
for efficient hydrogen production is shown in Fig. 7. Fig. 7. Advanced HI processing by an electro-electrodialysis device.
 S. Kubo et al. / Nuclear Engineering and Design 233 (2004) 355–362 361

Fig. 8. Mass and heat balance using an electrodialysis device.

The HIx solution from the Bunsen reaction is intro- The thermal load on HI processing drops in com-
duced into an electro-electrodialysis (EED) cell. EED parison with the conventional case. However, the extra
cells have two flow-channels, an anode and a cathode, thermal energy, about 169 kJ at an EED cell voltage of
which are separated by the cation exchange membrane. 0.35 V and an electricity generation efficiency of 0.4,
The same amount and composition of the solution is is required to drive the EED device for HI preconcen-
supplied to both sides, and the redox reactions given tration. If Hheat in Eq. (5) is placed on the sum of the
by following, occur on the electrodes. required heat and the extra heat, η is estimated to be
18.5%. The efficiency is increased by three times with-
2I− → I2 + 2e− (anode) (6) out heat recovery in comparison with the conventional
case. It is expected that more the heats recover from the
I2 + 2e− → 2I− (cathode) (7) removed heat, the higher the thermal efficiency gains.
On the cathode side, the HI molality of the HIx so-
lution increases to over-azeotropic composition to dis- Table 2
till only HI from the HIx solution. By separating HI Required and removed heat to drive the process
without water, the thermal burden for HI processing is Required Removed Extra heat
gradually reduced. heat (kJ) heat (kJ) (kJ)
Fig. 8 shows the mass and heat balance when the H2 SO4 processing 757.2 −472.6 –
EED device is employed. The required and removed HI processing 584.5 −503.7 169
Others 36 −115.4 –
heat to drive the process are given in Table 2.
362 S. Kubo et al. / Nuclear Engineering and Design 233 (2004) 355–362
5. Summary
JAERI has been conducting R&D on the IS process
for thermochemical hydrogen production using HTGR.
Following the completion of the present subjects, the
demonstration of continuous and closed-cycle opera-
tion, the improvement in the processing method of the
HIx solution and the selection of structural engineering
materials, we will proceed to pilot-scale tests as the
next R&D step. The pilot plant will feature high op-
erating pressure, practical materials for construction,
utilization of helium gas for heating and advanced HI
processing for high thermal efficiency. We will begin
making conceptual designs, flow sheets, basic engi-
neering, trial manufacture and simulation codes for the
plant from the beginning of Japanese FY2004. After
accomplishing detailed design, the construction of the
plant will start at the beginning of FY2006. The plant
will operate after FY2008.
Acknowledgement
The research and development in this paper were
conducted under contract between JAERI and Ministry
of Education, Culture, Sports, Science and Technology
of Japan.
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