Solar Energy 78 (2005) 632–646

www.elsevier.com/locate/solener

Analysis of sulfur–iodine thermochemical cycle

for solar hydrogen production. Part I: decomposition
of sulfuric acid
Cunping Huang, Ali T-Raissi *

Florida Solar Energy Center, University of Central Florida, 1679 Clearlake Road, Cocoa, FL 32922, USA
Received 16 July 2003; received in revised form 23 January 2004; accepted 26 January 2004
Available online 3 March 2004
Communicated by: Associate Editor S.A. Sherif

Abstract
The sulfur–iodine (S–I) thermochemical water splitting cycle is one of the most studied cycles for hydrogen (H2 )
production. S–I cycle consists of four sections: (I) acid production and separation and oxygen purification, (II) sulfuric
acid concentration and decomposition, (III) hydroiodic acid (HI) concentration, and (IV) HI decomposition and H2
purification. Section II of the cycle is an endothermic reaction driven by the heat input from a high temperature source.
Analysis of the S–I cycle in the past thirty years have been focused mostly on the utilization of nuclear power as the high
temperature heat source for the sulfuric acid decomposition step. Thermodynamic as well as kinetic considerations
indicate that both the extent and rate of sulfuric acid decomposition can be improved at very high temperatures (in
excess of 1000
C) available only from solar concentrators. The beneficial effect of high temperature solar heat for
decomposition of sulfuric acid in the S–I cycle is described in this paper. We used Aspen Technologies’ HYSYS
chemical process simulator (CPS) to develop flowsheets for sulfuric acid (H2 SO4 ) decomposition that include all mass
and heat balances. Based on the HYSYS analyses, two new process flowsheets were developed. These new sulfuric acid
decomposition processes are simpler and more stable than previous processes and yield higher conversion efficiencies
for the sulfuric acid decomposition and sulfur dioxide and oxygen formation.
 2004 Elsevier Ltd. All rights reserved.

Keywords: Solar thermochemical water splitting cycles; Sulfur–iodine cycle; Sulfuric acid decomposition

1. Introduction tigated. The sulfur–iodine cycle proposed by the General

Unlike electrolysis, thermochemical cycles for split-
ting water can convert low-level thermal energy directly
into chemical energy by forming hydrogen and oxygen,
and with overall first-law efficiencies exceeding 50%.
Since the conception of the first thermochemical cycle
in 1960s, a large number of water-splitting cycles have
been conceptualized and few of those extensively inves-
*
Corresponding author. Tel.: +1-321-638-1446; fax: +1-321-
638-1010.
E-mail address: ali@fsec.ucf.edu (A. T-Raissi).
0038-092X/$ - see front matter  2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.solener.2004.01.007
Atomics (GA) Company is one such cycle developed for
the large-scale hydrogen production.
The practicability of any thermochemical water
splitting cycle (TWSC) depends mainly on two factors:
(1) high overall thermal efficiency and (2) operational
feasibility. The overall thermal efficiency of a TWSC
determines the effectiveness of the cycle in receiving en-
ergy from a heat source and converting that into
chemical energy. For that, a highly endothermic reaction
is a prerequisite. Decomposition of sulfuric acid is one
such endothermic process and universally used in the
several high efficiency sulfur-family cycles including:
Marks 11 and 13 (developed at the Commission of the
 C. Huang, A. T-Raissi / Solar Energy 78 (2005) 632–646
Nomenclature
g thermal efficiency of the process
Qreaction overall reaction enthalpy of sulfuric acid
decomposition
European Communities Joint Research Center, Ispra,
Italy), GA and S–NH3 cycles. The feasibility of TWSCs
for large-scale industrial applications, on the other
hand, must be evaluated based on the environmental,
economic and operational considerations. One of the
important operational considerations is that a cycle
should be preferably a fluid based system (gas and/
or liquid) in order to facilitate efficient mass and
momentum transfer. One of the attractive features of
the sulfur-family cycles in general, and GA S–I cycle in
particular, is that they are fluid-based processes.
The GA cycle consists of four sections: (I) acid pro-
duction and separation and oxygen purification, (II)
sulfuric acid concentration and decomposition, (III)
hydroiodic acid (HI) concentration, and (IV) HI
decomposition and H2 purification. Section II of GA
cycle is an endothermic process driven by the heat input
from a high temperature source. Analysis of this cycle in
the past thirty years have been focused mostly on the
utilization of nuclear power as the high temperature heat
source for performing the decomposition of sulfuric
acid. Thermodynamic as well as kinetic considerations
indicate that both the extent and rate of sulfuric acid
decomposition can be improved at very high tempera-
tures (in excess of 1000
C) available only from solar
concentrators.
A complete flowsheet of the S–I cycle is rarely seen in
the scientific literature. However, extensive flowsheet
analysis of the concentration and decomposition of
sulfuric acid part (Section II) of the cycle has been car-
ried out. In this paper, we present HYSYS simulation
results for Section II of the S–I TWSC and based on
that, formulate two new and simpler processes for the
S–I thermochemical cycle for splitting water.
2. Decomposition of sulfuric acid
The S–I cycle consists of three steps:
H2 SO4 ðgÞ ¼ SO2 ðgÞ þ H2 OðgÞ þ 0:5O2 ðgÞ 850
C
ð1Þ
I2 ðlÞ þ SO2 ðaqÞ þ 2H2 OðlÞ
¼ 2HIðlÞ þ H2 SO4 ðaqÞ 120
C ð2Þ
2HIðlÞ ¼ I2 ðlÞ þ H2 ðgÞ 450
C ð3Þ
633
Qi heat or electrical energy flow calculated for
unit operations
Based on the chemical engineering considerations, it is
possible to separate the cycle into four sections (Norman
et al., 1982; Besenbruch, 1982; Hammache and Bilgen,
€ urk et al., 1994, 1995):
1992; Ozt€
I Acid production and separation with O2 purification.
II H2 SO4 concentration and decomposition.
III HI concentration and
IV HI decomposition and H2 purification.
Section II is the most thoroughly investigated part of
the S–I TWSC since it constitutes the heart of the cycle,
and it is generally accepted that the efficiency of the
whole process depends on the efficiency of H2 SO4
decomposition. The newest and most efficient flowsheet
€ urk et al., 1995––i.e. Bilgen’s
was published in 1995 (Ozt€
flowsheet, in this paper) with energetic and exergetic
efficiencies of 76.0% and 75.6%, respectively. Bilgen’s
flowsheet was based on the chemical equilibrium calcu-
lations for sulfuric acid decomposition. Moreover, the
following three assumptions were used: (1) all single
phase gases were considered as being ideal gases, while
liquid phases of H2 O(l) and H2 SO4 (l) assumed to be real
solutions; (2) all gas mixtures were considered as ideal
gas mixtures and H2 O(l) and H2 SO4 (l) as real solutions;
and (3) Henry’s law was used for the mixture of H2 O(l)
and SO2 . Bilgen’s is somewhat complicated but can be
simplified without reducing the cycle efficiency and/or
process feasibility.
Section II in the S–I TWSC contains two important
steps: sulfuric acid purification and decomposition.
Purification step is important because if a high purity
of sulfuric acid can be obtained before the stream
enters the acid decomposition unit operation, the de-
composition step can be carried out with high efficiency.
In the Bilgen’s flowsheet, five separators, three eva-
porators and an absorption column are used to
accomplish H2 SO4 purification. It is possible that some
of these unit operations will not function as theo-
rized. Based on a non-idealized HYSYS simulation for
the Bilgen’s flowsheet, two new processes are pro-
posed using a distillation column as a main separa-
tion unit. The distillation column is used because it
combines the function of a highly efficient separator
with a highly efficient heat exchanger. Material streams
can be directly mixed and readily re-distributed in a
distillation column.
634 C. Huang, A. T-Raissi / Solar Energy 78 (2005) 632–646
3. HYSYS simulation code
We employed the steady state HYSYS CPS to sim-
ulate Section II of the S–I TWSC. Flow package selec-
tion, reactor choice and kinetic modeling are three main
elements of this effort. The species involved in Section II
analysis are sulfuric acid, water, oxygen, sulfur dioxide
and sulfur trioxide. A non-idealized system is used for
this simulation, requiring selection of a proper fluid
package. In HYSYS, all necessary information pertain-
ing to pure component flash and physical property cal-
culations are contained within the fluid packages.
Therefore, the selection of a fluid package for a given
system becomes a very critical issue. For oil, gas and
petrochemical applications, the Peng–Robinson (P–R)
equation of state is generally used (HYSYS 3.01, 2002).
Hyprotech’s enhancements to P–R equation of state
enable it to be accurate for a variety of mixtures over a
wide range of conditions. P–R equation of state as
implemented by HYSYS can be used to solve most
single phase, two phase and three-phase systems with a
high degree of efficiency and reliability (HYSYS 3.01,
2002). We also used the PRSV equation of state as a
fluid package to solve for the sulfuric acid states, which
means that no idealized assumptions were needed.
HYSYS simulation of the decomposition of sulfuric
acid was carried out in two steps. In the first step, sul-
furic acid was assumed to decompose into water and
sulfur trioxide. In the second step, sulfur trioxide
decomposes to produce oxygen and sulfur dioxide
according to the following reactions:
0 cess. After vaporization, low-pressure (8 kPa) water
H2 SO4 ðgÞ ¼ H2 OðgÞ þ SO3 ðgÞ DH298 ¼ 97:54 kJ=mol
ð4Þ
0
SO3 ðgÞ ¼ SO2 ðgÞ þ 0:5O2 ðgÞ DH298 ¼ 98:92 kJ=mol
ð5Þ
Reactions (4) and (5) can occur simultaneously, i.e. once
sulfur trioxide is produced from sulfuric acid decom-
position it will immediately decompose to sulfur trioxide
and oxygen. To simplify the process we assume that the
two reactions can be separated and processed in two
separate reactors. Since no kinetic rate equations are
available for Eq. (4), one has to resort to making some
assumptions. Equilibrium calculations indicate that
close to 100% H2 SO4 decomposition is achieved at
temperatures exceeding 700
C. Over 90% conversion
for sulfuric acid decomposition is assumed in our
HYSYS simulation of reaction (4). To simplify thermal
efficiency calculations, the reaction enthalpy for reaction
(4) was assumed to be equal to that for reaction (5)
calculated by HYSYS. The rate equation for the
decomposition of sulfur trioxide (SO3 ) was based on:
rrxn ¼ kt CSO3 (Spewock et al., 1976) fitting to a plug
flow reactor model in HYSYS, whereas the reaction rate
constant: kt ¼ A expðEa =RT Þ. For SO3 decomposition
in the presence of catalyst WX-2, the activation energy
and pre-exponential factor assumed to be 17.46 kcal/
mol/K, and 2.45 · 108 h1 , respectively. No heat losses
were assumed for the reactors and heat exchangers in the
flowsheet. The stage efficiency of the distillation column
was 95%. In addition, for reaction: SO3 (g) + H2 O(l) ¼
H2 SO4 (g), 100% conversion efficiency was assumed in
the distillation and absorption columns, meaning that
both SO3 and H2 SO4 were recovered through the col-
umns and sent back to the two decomposition reactors
(where reactions 4 and 5 take place) to produce sulfur
dioxide and oxygen.
4. Results and discussion
€ urk et al., 1994, 1995)
4.1. Bilgen’s flowsheet (Ozt€
A HYSYS flowsheet based on the Bilgen’s for sulfur
acid decomposition is depicted in Fig. 1. To increase
process efficiency, the gas–liquid separation must be
carried out at high efficiency so that sulfuric acid at high
purity enters the decomposition reactor. Thus, the gen-
eral flowsheet can be separated into three subsections as
follows:
(a) Sulfuric acid concentration, streams 1–14. A ser-
ies of chemical engineering unit operations (separators
S1, S2 and S3) are employed to vaporize and separate
water from H2 SO4 solution for heat recovery and boil-
ing water during the sulfuric acid decomposition pro-
vapor is condensed, and then the liquid water is pumped
out of the system.
(b) Sulfuric acid decomposition, streams 16–18. Two
plug flow reactors are employed to carry out sulfuric
acid decomposition in successive steps according to
reactions (4) and (5). First, H2 SO4 is decomposed into
sulfur trioxide and water and then the former is further
decomposed into sulfur dioxide and oxygen. To study
the temperature effect on the decomposition, the mate-
rial stream is heated to an appropriate temperature in
the inlet of the secondary decomposer. The energy re-
quired for heating the stream 16-1 is provided by heat
stream EE. The outlet temperature in the second
decomposition reactor is set to be the same as inlet
temperature so that the reaction occurs under an iso-
thermal condition. The heat requirement for the
decomposition is R2 as shown in Fig. 1.
(c) Gas separation and heat recovery. Beginning with
streams 19–13 and 27 and continuing as follows: an
absorber is used to capture the residual acid and sulfur
trioxide, which is then sent back to the decomposers.
Before water in stream 27 is separated out in S4, it
passes through the heat exchanger HX2 to allow some
heat recovery, and finally is collected and exits as stream
 C. Huang, A. T-Raissi / Solar Energy 78 (2005) 632–646
Fig. 1. HYSYS simulation for sulfuric acid decomposition based on Bilgen’s flowsheet (Hammache and Bilgen, 1992).
47. The gaseous phase in stream 29, containing mostly
sulfur dioxide and oxygen, passes through a series of
heat exchangers (HX1-1, HX6, HX5), a separator (S5)
and an expander (EXP) and exits as stream 35. The
sulfuric acid conversion and the yields of oxygen and
sulfur dioxide formation are determined by calculating
H2 SO4 , O2 and SO2 concentration in the streams 1, 35
and 47.
Mass balance and stream composition for sulfur tri-
oxide decomposition in reactor 2 at 850 and 750
C,
including individual species’ flow rate, total flow rate,
vapor fraction, stream temperatures and pressures are
given in Tables 1 and 2, respectively. The data are cal-
culated using non-idealized thermodynamics and there-
fore simulate close to real chemical process conditions.
Our calculations show that some of the unit operations,
such as heat exchangers and separators, in Bilgen’s
flowsheet are not needed and may be eliminated to
simplify the process. For example, the molar flow rate
for stream 10 is 0.06614 kg mol/h, consisting of about
1.2% of input flow (5.40530 kmol/h in stream 1) that is
split into streams, 21 and 22. Stream 21 is compressed
and passed through two heat exchangers for heat
recovery. However, due to the low temperature and low
flow rate, the extent of heat recovery is very small.
The extent of sulfuric acid decomposition and the
yield of sulfur dioxide and oxygen are calculated from
the flowsheet mass balance, and results are given in Fig.
2. When the decomposition temperatures remain above
750
C, the process remains stable with sulfuric acid
conversions close to 100% with about 98% sulfur dioxide
yield. Results of Fig. 2 depict that when the reaction
temperatures are lower than 730
C, the extent of H2 SO4
conversion and SO2 /O2 yields drop dramatically. In
635
addition, the results indicate that as the H2 SO4 decom-
position temperatures are lowered, the concentration of
sulfur trioxide in the stream 19 are increased. The high
H2 SO4 concentration in stream 14 at the exit of
adsorption tower results in a higher unconverted sulfur
trioxide concentration, leading to elevated absorber
temperature and higher temperature in stream 14
resulting in the steady state operation to cease.
Unlike Bilgen’s flowsheet, the HYSYS simulation is
based on a more realistic plant design that uses reac-
tion kinetics and non-idealized process condition. Unit
operations in the HYSYS program are calculated using
real chemical engineering data. The HYSYS flowsheet
results for the mass balances can be used directly for
plant sizing and process optimization. For example,
flow rates from HYSYS flowsheet calculated in units of
kg mol/h can be scaled up to min/min or even/s, if
needed. Especial care must be taken when using dif-
ferent rate equations and the selection of different
reaction resident times. The latter is determined based
on the volumetric flow rate and the reactor volume. As
noted before, one of our main objectives was to assess
the mass balances, thermal efficiency and stability of
the S–I TWSC flowsheet. Therefore, we selected a rel-
atively low spatial velocity for carrying out HYSYS
simulation. For example, when the decomposition
temperature of sulfur trioxide is 850
C, the molar flow
rate in stream 17 is 2.1274/h, corresponding to a mass
flow rate of 104.36 kg/h and the actual volumetric flow
rate of 16.566 m3 /h as calculated by HYSYS. The
volume of SO3 decomposition reactor (R2) is 0.25 m3
resulting in a spatial velocity of 16.566/0.25 ¼ 66.3 h1
and resident time of 54.3 s. A more detailed discussion
on evaluation of the kinetic rate equations for sulfur
636 C. Huang, A. T-Raissi / Solar Energy 78 (2005) 632–646

Table 1
Mass balance and stream composition for Bilgen’s flowsheet (sulfur trioxide decomposition temperature 850
C)
Stream no. Composition mole flow (kmol/h) Mole flow Vapor Tempera- Pressure
O2 H2 O SO2 SO3 H2 SO4 (kmol/h) fraction ture (
C) (kPa)

1 0.00000 4.34370 0.00400 0.00000 1.05760 5.40530 0.0020 119.90 180.0

2 0.00000 4.34370 0.00400 0.00000 1.05760 5.40530 0.7526 74.05 8.0
3 0.00000 4.06400 0.00400 0.00000 0.00000 4.06800 1.0000 74.05 8.0
4 0.00000 0.27974 0.00000 0.00000 1.65760 1.93734 0.0000 74.05 8.0
(5-1) 0.00000 0.27974 0.00000 0.00000 1.65760 1.93734 0.1264 94.30 8.0
5 0.00000 0.27974 0.00000 0.00000 1.65760 1.93734 0.1266 94.35 8.0
6 0.00000 0.16929 0.00000 0.00000 0.00000 0.16929 1.0000 94.35 8.0
7 0.00000 0.11045 0.00000 0.00000 1.05760 1.16805 0.0000 94.35 8.0
8 0.00000 0.11045 0.00000 0.00000 1.05760 1.16805 0.0000 94.35 20.0
9 0.00000 0.11045 0.00000 0.00000 1.05760 1.16805 0.0566 151.90 20.0
10 0.00000 0.06614 0.00000 0.00000 0.00000 0.06614 1.0000 151.90 20.0
11 0.00000 0.04431 0.00000 0.00000 1.05760 1.10191 0.0000 151.90 20.0
12 0.00000 0.04431 0.00000 0.00000 1.05760 1.10191 0.0000 151.80 1200.0
13 0.52892 1.10210 1.05790 0.00000 0.00000 2.68892 1.0000 201.00 1200.0
14 0.00000 0.00586 0.00014 0.00000 1.06300 1.06900 0.0000 226.00 30.0
15 0.00000 0.00586 0.00014 0.00000 1.06300 1.06900 0.0000 226.00 1200.0
16 0.00000 0.00586 0.00014 0.00000 1.06300 1.06900 0.0000 384.20 1200.0
16-1 0.00000 1.06330 0.00014 1.05760 0.00535 2.12640 0.9988 335.30 1200.0
17 0.00000 1.06330 0.00014 1.05760 0.00535 2.12640 1.0000 850.00 1200.0
18-1 0.52881 1.06330 1.05780 0.00027 0.00535 2.65553 1.0000 850.00 1200.0
18 0.52881 1.06330 1.05780 0.00027 0.00535 2.65553 1.0000 850.00 1200.0
19 0.52881 1.06330 1.05780 0.00027 0.00535 2.65553 1.0000 420.40 1200.0
20 0.00000 0.06614 0.00000 0.00000 0.00000 0.06614 1.0000 85.00 20.0
21 0.00000 0.04630 0.00000 0.00000 0.00000 0.04630 1.0000 85.00 20.0
22 0.00000 0.01984 0.00000 0.00000 0.00000 0.01984 1.0000 85.00 20.0
23 0.00000 0.01984 0.00000 0.00000 0.00000 0.01984 1.0000 256.66 83.2
24 0.00000 0.01984 0.00000 0.00000 0.00000 0.01984 1.0000 135.00 83.2
25 0.00000 0.01984 0.00000 0.00000 0.00000 0.01984 1.0000 95.00 83.2
25-1 0.00000 0.01984 0.00000 0.00000 0.00000 0.01984 0.0000 74.00 83.2
26 0.00000 0.01984 0.00000 0.00000 0.00000 0.01984 0.0000 74.06 570.0
27 0.52892 1.10210 1.05790 0.00000 0.00000 2.68892 0.8521 139.90 1200.0
28 0.00003 0.38781 0.00994 0.00000 0.00000 0.39778 0.0000 139.90 1200.0
29 0.52888 0.71432 1.04790 0.00000 0.00000 2.29110 1.0000 139.90 1200.0
30 0.52888 0.71432 1.04790 0.00000 0.00000 2.29110 0.8557 124.90 1200.0
31 0.00003 0.32006 0.01045 0.00000 0.00000 0.33054 0.0000 124.90 1200.0
32 0.52889 0.39425 1.03750 0.00000 0.00000 1.96064 1.0000 124.90 1200.0
33 0.52889 0.39425 1.03750 0.00000 0.00000 1.96064 1.0000 125.90 1200.0
34 0.52889 0.39425 1.03750 0.00000 0.00000 1.96064 0.9434 69.29 200.0
35 0.52889 0.39425 1.03750 0.00000 0.00000 1.96064 0.9450 69.51 200.0
36 0.00000 4.23320 0.00400 0.00000 0.00000 4.23720 1.0000 74.86 8.0
37 0.00000 4.23320 0.00400 0.00000 0.00000 4.23720 0.0000 41.55 20.0
38 0.00000 4.23320 0.00400 0.00000 0.00000 4.23720 0.0000 41.61 570.0
39 0.00000 0.04630 0.00000 0.00000 0.00000 0.04630 0.0000 59.00 20.0
40 0.00000 0.04630 0.00000 0.00000 0.00000 0.04630 0.0000 59.04 570.0
41 0.00003 0.32006 0.01045 0.00000 0.00000 0.33054 0.0008 93.05 570.0
42 0.00003 4.59960 0.01445 0.00000 0.00000 4.61408 0.0000 45.55 570.0
43 0.00003 0.38781 0.00994 0.00000 0.00000 0.39778 0.0000 126.40 1200.0
44 0.00003 0.38781 0.00994 0.00000 0.00000 0.39778 0.0142 126.40 570.0
45 0.00006 5.00730 0.02439 0.00000 0.00000 5.03174 0.0000 52.54 570.0

trioxide decomposition is deferred to another paper.
Choosing a longer resident time has the advantage of
reducing the data fluctuations that is the result of mass
balance varying greatly as different rate equations are
used.
Table 3 depicts the energy requirements for various
unit operations for a range of decomposition tempera-
tures from 720 to 1200
C. Thermal efficiency ðgÞ of the
process is calculated according to (Hammache and Bil-
gen, 1992):
 C. Huang, A. T-Raissi / Solar Energy 78 (2005) 632–646 637

Table 2
Mass balance and stream composition for Bilgen’s flowsheet (sulfur trioxide decomposition temperature 750
C)
Stream no. Composition mole flow (kmol/h) Mole flow Vapor Tempera- Pressure
O2 H2 O SO2 SO3 H2 SO4 (kmol/h) fraction ture (
C) (kPa)

1 0.00000 4.34370 0.00400 0.00000 1.05760 5.40530 0.0020 119.90 180.0

2 0.00000 4.34370 0.00400 0.00000 1.05760 5.40530 0.7526 74.05 8.0
3 0.00000 4.06400 0.00400 0.00000 0.00000 4.06800 1.0000 74.05 8.0
4 0.00000 0.27974 0.00000 0.00000 1.65760 1.93734 0.0000 74.05 8.0
(5-1) 0.00000 0.27974 0.00000 0.00000 1.05760 1.33734 0.1264 94.30 8.0
5 0.00000 0.27974 0.00000 0.00000 1.05760 1.33734 0.1266 94.35 8.0
6 0.00000 0.16929 0.00000 0.00000 0.00000 0.16929 1.0000 94.35 8.0
7 0.00000 0.11045 0.00000 0.00000 1.05760 1.16805 0.0000 94.35 8.0
8 0.00000 0.11045 0.00000 0.00000 1.05760 1.16805 0.0000 94.35 20.0
9 0.00000 0.11045 0.00000 0.00000 1.05760 1.16805 0.0566 151.90 20.0
10 0.00000 0.06614 0.00000 0.00000 0.00000 0.06614 1.0000 151.90 20.0
11 0.00000 0.04431 0.00000 0.00000 1.05760 1.10191 0.0000 151.90 20.0
12 0.00000 0.04431 0.00000 0.00000 1.05760 1.10191 0.0000 151.80 1200.0
13 0.52892 1.01021 1.05790 0.00000 0.00000 2.59703 1.0000 201.20 1200.0
14 0.00000 0.00568 0.00014 0.00000 1.06300 1.06883 0.0000 226.00 30.0
15 0.00000 0.00568 0.00014 0.00000 1.06300 1.06883 0.0000 226.00 1200.0
16 0.00000 0.00568 0.00014 0.00000 1.06300 1.06883 0.0000 347.50 1200.0
16-1 0.00000 1.04080 0.00014 1.03510 0.02789 2.10394 0.9851 283.90 1200.0
17 0.00000 1.04080 0.00014 1.03510 0.02789 2.10394 1.0000 750.00 1200.0
18-1 0.51754 1.04080 1.03520 0.00000 0.02792 2.62146 1.0000 750.00 1200.0
18 0.51735 1.04040 1.03480 0.00000 0.02828 2.62083 1.0000 750.00 1200.0
19 0.51735 1.04040 1.03480 0.00000 0.02828 2.62083 1.0000 420.40 1200.0
20 0.00000 0.06614 0.00000 0.00000 0.00000 0.06614 1.0000 85.00 20.0
21 0.00000 0.04630 0.00000 0.00000 0.00000 0.04630 1.0000 85.00 20.0
22 0.00000 0.01984 0.00000 0.00000 0.00000 0.01984 1.0000 85.00 20.0
23 0.00000 0.01984 0.00000 0.00000 0.00000 0.01984 1.0000 256.70 83.2
24 0.00000 0.01984 0.00000 0.00000 0.00000 0.01984 1.0000 135.00 83.2
25 0.00000 0.01984 0.00000 0.00000 0.00000 0.01984 1.0000 95.00 83.2
25-1 0.00000 0.01984 0.00000 0.00000 0.00000 0.01984 0.0000 74.00 83.2
26 0.00000 0.01984 0.00000 0.00000 0.00000 0.01984 0.0000 74.00 570.0
27 0.52892 1.01021 1.05790 0.00000 0.00000 2.59703 0.8521 139.90 1200.0
28 0.00003 0.38781 0.00994 0.00000 0.00000 0.39778 0.0000 139.90 1200.0
29 0.52888 0.71432 1.04790 0.00000 0.00000 2.29110 1.0000 139.90 1200.0
30 0.52888 0.71432 1.04790 0.00000 0.00000 2.29110 0.8557 124.90 1200.0
31 0.00003 0.32006 0.01045 0.00000 0.00000 0.33054 0.0000 124.90 1200.0
32 0.52886 0.39425 1.03750 0.00000 0.00000 1.96061 1.0000 124.90 1200.0
33 0.52886 0.39425 1.03750 0.00000 0.00000 1.96061 1.0000 125.90 1200.0
34 0.52886 0.39425 1.03750 0.00000 0.00000 1.96061 0.9434 69.29 200.0
35 0.52886 0.39425 1.03750 0.00000 0.00000 1.96061 0.9450 69.51 200.0
36 0.00000 4.02332 0.00400 0.00000 0.00000 4.02732 1.0000 74.86 8.0
37 0.00000 4.02332 0.00400 0.00000 0.00000 4.02732 0.0000 41.55 20.0
38 0.00000 4.02332 0.00400 0.00000 0.00000 4.02732 0.0000 41.61 570.0
39 0.00000 0.04630 0.00000 0.00000 0.00000 0.04630 0.0000 59.00 20.0
40 0.00000 0.04630 0.00000 0.00000 0.00000 0.04630 0.0000 59.04 570.0
41 0.00003 0.32006 0.01045 0.00000 0.00000 0.33054 0.0008 93.05 570.0
42 0.00003 4.59960 0.01445 0.00000 0.00000 4.61408 0.0000 45.55 570.0
43 0.00003 0.38781 0.00994 0.00000 0.00000 0.39778 0.0000 126.40 1200.0
44 0.00003 0.38781 0.00994 0.00000 0.00000 0.39778 0.0142 126.40 570.0
45 0.00006 5.00730 0.02439 0.00000 0.00000 5.03174 0.0000 52.54 570.0

Qreaction and sulfur dioxide. In the HYSYS simulation flow-

g¼ P
Qi sheet, it is the sum of heat requirement for reactors R1
and R2. Qi is heat or electrical energy flow calculated
where Qreaction is the overall reaction enthalpy for for individual unit operations. Due to low temperatures
decomposing sulfuric acid to produce water, oxygen and low flow rates involved, the heat rejects from
638
110
100
Conversion & yield (%)
90
80
70
60
50
40
30
20
10
650
condensers CE1 to CE4 are essentially waste heat and
therefore not included in the total heat balance. Ex-
pander energy recovery is assumed at 50% efficiency.
The heat flow required for the operation of pumps P1
to P6 and compressor COE was determined assuming
30% conversion efficiency from heat to electric power.
For example, if the electrical energy for P1 is 0.935 kJ/
h, then the heat flow was calculated as 0.935/0.30, or
3.12 kJ/h. The total heat flow and thermal efficiencies
for decomposing sulfuric acid at various temperatures
are given in Table 3. When decomposition temperature
is above 750
C, the thermal efficiencies vary between
76% to about 77%. Note that this calculation is based
on the assumption that Reactions (4) and (5) require
the same amount of input energy. This assumption is
valid because the reaction enthalpies for reactions (4)
and (5) are nearly the same and compared to the large
amounts of waste heat rejected in other unit opera-
tions, any discrepancies here is negligible. For a reac-
tion temperature of 850
C, the 76.6% thermal
efficiency calculated based on the new flowsheet is very
close to the 76.0% reported by Hammache and Bilgen
(1992). High efficiencies depicted in Table 3 support
Bilgen’s approach and indicate that the acid decom-
position step can be carried out as a highly endother-
mic process in S–I TWSCs. In addition, the process
stability over a wide temperature range shows great
promise for the possible utilization of solar energy as a
heat source for the S–I TWSCs sulfuric acid decom-
position step.
4.2. Improved process (flowsheet I) for sulfuric
acid decomposition step
HYSYS simulation shows that Bilgen’s flowsheet can
be very efficient for the small-scale decomposition of
sulfuric acid. This is due to integrated unit operations
can be used including combined vaporization and sep-
aration unit operation that increases the sulfuric acid
C. Huang, A. T-Raissi / Solar Energy 78 (2005) 632–646
O2 yield SO2 yield H2SO4 Conversion
750 850 950 1050 1150 1250
Temperature (°C)
Fig. 2. Temperature stability of Bilgen’s flowsheet.
concentration before it undergoes decomposition. Bil-
gen’s flowsheet may be too complicated for the large-
scale applications. The flowsheet as depicted in Fig. 1,
uses four separators and three vaporizers to remove
water from sulfuric acid. The flowsheet may be simpli-
fied by eliminating some of the heat exchangers and
condensers in the process flowsheet without affecting the
performance. We have devised an improved process
flowsheet based on the HYSYS analyses of Bilgen’s as
shown in Fig. 3.
In the revised flowsheet I, we have included a distil-
lation column to separate water from sulfuric acid
solution. In the revised process I, the material streams
mix directly to allow heat recovery and re-distribution
via distillation column. To reduce the heat requirement,
pressures at the reboiler and condenser are 100 and 450
kPa, respectively. Tables 4–7 summarize the mass bal-
ance for the flowsheet I depicting the effect of distillation
column employed. Simulation results in Tables 4–7 de-
pict species concentration and molar flow rate for all
streams in the flowsheet I as a function of decomposition
temperature in the SO3 reactor varied in the range of
500–1200
C. Results indicate that it is possible to sep-
arate the sulfuric acid in the distillation column and
recycle it back into the acid decomposition reactors for
further reaction and conversion into oxygen and sulfur
dioxide. Fig. 4 depicts the sulfuric acid conversions and
yields of O2 and SO2 produced as a function of SO3
decomposition temperature. Comparing results from
Fig. 4 to that of Fig. 3 (for Bilgen’s process), we observe
an improvement in both H2 SO4 conversion as well as
process stability when the revised flowsheet I is used.
The insensitivity of H2 SO4 conversion to the decompo-
sition temperature, calculated for a wide temperature
range (500–1200
C), makes the revised flowsheet I more
suitable process for use with a transient energy source
such as solar energy.
The heat exchanges calculated for all of the flow-
sheet I unit operations and overall process efficiencies
Table 3
Energy flow for sulfuric acid decomposition section (Fig. 2)

C. Huang, A. T-Raissi / Solar Energy 78 (2005) 632–646

Unit operations Heat or energy flow (kJ/h)
720
C 750
C 800
C 850
C 900
C 950
C 1000
C 1050
C 1100
C 1200
C
Pump (PE1) 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9
Pump (PE2) 93.0 93.0 93.0 93.0 93.0 93.0 93.0 93.0 93.0 93.0
Pump (PE3) 171.4 95.0 96.1 95.0 94.5 94.4 94.4 94.4 94.4 94.4
Pump (PE4) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Pump (PE5) 56.4 56.4 56.4 56.4 56.4 56.4 56.4 56.4 56.4 56.4
Pump (PE6) 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6
Cooler (CE1) )187,400 )187,400 )187,400 )187,400 )187,400 )187,400 )187,400 )187,400 )187,400 )187,000
Cooler (CE2) )2125 )2006 )2024 )2010 )2024 )2024 )2024 )2024 )2024 )2024
Cooler (CE3) )844 )844 )844 )844 )844 )844 )844 )844 )844 )844
Cooler (CE4) )12,520 )415 )415 )415 )415 )415 )415 )415 )415 )415
Heater (HE) 137,100 61,650 64,240 64,600 64,900 65,190 65,510 65,760 66,020 66,520
Comp. (COE) 118 118 118 118 118 118 118 118 118 118
Turbine (EXP) )14,010 )7754 )8012 )8010 )8014 )8012 )8014 )8012 )8012 )8012
Reactor (R1) 81,040 99,600 101,400 101,100 100,800 100,500 100,200 99,900 99,650 99,210
Reactor (R2) 81,040 99,600 101,400 101,100 100,800 100,500 100,200 99,900 99,650 99,210

Total heat flow 293,643 258,187 264,251 264,009 263,705 263,396 263,115 262,766 262,526 262,146

Efficiency (%) 55.2 77.2 76.7 76.6 76.4 76.3 76.2 76.0 75.9 75.7

639
640 C. Huang, A. T-Raissi / Solar Energy 78 (2005) 632–646

Fig. 3. Improved HYSYS simulation flowsheet I.

Table 4
Mass balance and stream composition for revised flowsheet I (sulfur trioxide decomposition temperature: 500
C)
Stream no. Composition mole flow (kmol/h) Mole flow Vapor Tempera- Pressure
O2 H2 O SO2 SO3 H2 SO4 (kmol/h) fraction ture (
C) (kPa)

1 0.00000 4.34370 0.00400 0.00000 1.05760 5.40530 0.00000 119.90 180.0

2 0.00000 4.34370 0.00400 0.00000 1.05760 5.40530 0.00000 119.90 570.0
3 0.52899 5.40172 1.05728 0.00000 0.00000 6.98800 1.00000 138.40 450.0
4 0.00000 0.00703 0.00000 0.00000 1.39897 1.40600 0.00000 396.60 100.0
5 0.00000 0.00703 0.00000 0.00000 1.39897 1.40600 0.00000 462.00 1200.0
6 0.00000 0.00703 0.00000 0.00000 1.39897 1.40600 0.00000 507.50 1200.0
7 0.00000 1.06469 0.00000 1.05780 0.34151 2.46400 0.84200 276.80 1200.0
8 0.00000 1.06469 0.00000 1.05780 0.34151 2.46400 1.00000 500.00 1200.0
9 0.52869 1.06455 1.05737 0.00000 0.34139 2.99200 1.00000 500.00 1200.0
10 0.52869 1.06455 1.05737 0.00000 0.34139 2.99200 0.95300 419.10 570.0
11 0.52869 1.06455 1.05737 0.00000 0.34139 2.99200 0.95300 419.10 570.0
12 0.52899 5.40172 1.05728 0.00000 0.00000 6.98800 0.26630 70.00 180.0
13 0.52890 0.32791 1.00420 0.00000 0.00000 1.86100 1.00000 70.00 180.0
14 0.00000 5.07317 0.05332 0.00000 0.00000 5.12649 0.00000 70.00 180.0

Table 5
Mass balance and stream composition for revised flowsheet I (sulfur trioxide decomposition temperature: 650
C)
Stream no. Composition mole flow (kmol/h) Mole flow Vapor Tempera- Pressure
O2 H2 O SO2 SO3 H2 SO4 (kmol/h) fraction ture (
C) (kPa)

1 0.00000 4.34370 0.00400 0.00000 1.05760 5.40530 0.00000 119.90 180.0

2 0.00000 4.34370 0.00400 0.00000 1.05760 5.40530 0.00000 119.90 570.0
3 0.52899 5.40172 1.05728 0.00000 0.00000 6.98800 1.00000 138.40 450.0
4 0.00000 0.00635 0.00000 0.00000 1.26266 1.26900 0.00000 369.50 100.0
5 0.00000 0.00635 0.00000 0.00000 1.26266 1.26900 0.00000 396.60 1200.0
6 0.00000 0.00635 0.00000 0.00000 1.26266 1.26900 0.00000 490.00 1200.0
7 0.00000 1.06414 0.00000 1.05785 0.20501 2.32700 0.90240 296.60 1200.0
8 0.00000 1.06414 0.00000 1.05785 0.20501 2.32700 1.00000 650.00 1200.0
9 0.52875 1.06377 1.05749 0.00000 0.20499 2.85500 1.00000 650.00 1200.0
10 0.52875 1.06377 1.05749 0.00000 0.20499 2.85500 0.98400 412.40 570.0
11 0.52875 1.06377 1.05749 0.00000 0.20499 2.85500 0.98400 412.40 570.0
12 0.52899 5.40172 1.05728 0.00000 0.00000 6.98800 0.26630 70.00 1800.0
13 0.52890 0.32791 1.00420 0.00000 0.00000 1.86100 1.00000 70.00 180.0
14 0.00000 5.07368 0.05332 0.00000 0.00000 5.12700 0.00000 70.00 180.0
 C. Huang, A. T-Raissi / Solar Energy 78 (2005) 632–646 641

Table 6
Mass balance and stream composition for revised flowsheet I (sulfur trioxide decomposition temperature: 750
C)
Stream no. Composition mole flow (kmol/h) Mole flow Vapor Tempera- Pressure
O2 H2 O SO2 SO3 H2 SO4 (kmol/h) fraction ture (
C) (kPa)

1 0.00000 4.34370 0.00400 0.00000 1.05760 5.40530 0.00000 119.90 180.0

2 0.00000 4.34370 0.00400 0.00000 1.05760 5.40530 0.00000 119.90 570.0
3 0.52899 5.40172 1.05728 0.00000 0.00000 6.98800 1.00000 138.40 450.0
4 0.00000 0.00600 0.00000 0.00000 1.19301 1.19900 0.00000 396.50 100.0
5 0.00000 0.00600 0.00000 0.00000 1.19301 1.19900 0.00000 396.60 1200.0
6 0.00000 0.00600 0.00000 0.00000 1.19301 1.19900 0.00000 507.00 1200.0
7 0.00000 1.06348 0.00000 1.05761 0.13491 2.25600 0.93520 313.10 1200.0
8 0.00000 1.06348 0.00000 1.05761 0.13491 2.25600 1.00000 750.00 1200.0
9 0.52887 1.06359 1.05774 0.00000 0.13479 2.78500 1.00000 750.00 1200.0
10 0.52887 1.06359 1.05774 0.00000 0.13479 2.78500 1.00000 418.40 570.0
11 0.52887 1.06359 1.05774 0.00000 0.13479 2.78500 1.00000 418.40 570.0
12 0.52899 5.40172 1.05728 0.00000 0.00000 6.98800 0.26630 70.00 1800.0
13 0.52890 0.32791 1.00420 0.00000 0.00000 1.86100 1.00000 70.00 180.0
14 0.00000 5.07368 0.05332 0.00000 0.00000 5.12700 0.00000 70.00 180.0

Table 7
Mass balance and stream composition for revised flowsheet I (sulfur trioxide decomposition temperature: 850
C)
Stream no. Composition mole flow (kmol/h) Mole flow Vapor Tempera- Pressure
O2 H2 O SO2 SO3 H2 SO4 (kmol/h) fraction ture (
C) (kPa)

1 0.00000 4.34370 0.00400 0.00000 1.05760 5.40530 0.00000 119.90 180.0

2 0.00000 4.34370 0.00400 0.00000 1.05760 5.40530 0.00000 119.90 570.0
3 0.52899 5.40172 1.05728 0.00000 0.00000 6.98800 1.00000 138.40 450.0
4 0.00000 0.00600 0.00000 0.00000 1.19301 1.19900 0.00000 396.50 100.0
5 0.00000 0.00600 0.00000 0.00000 1.19301 1.19900 0.00000 396.60 1200.0
6 0.00000 0.00600 0.00000 0.00000 1.19301 1.19900 0.00000 538.00 1200.0
7 0.00000 1.06306 0.00000 1.05743 0.04151 2.16200 0.98370 358.60 1200.0
8 0.00000 1.06306 0.00000 1.05743 0.04151 2.16200 1.00000 850.00 1200.0
9 0.20371 2.08014 0.40742 0.00000 0.13479 2.82606 1.00000 850.00 1200.0
10 0.20371 2.08014 0.40742 0.00000 0.13479 2.82606 1.00000 412.40 570.0
11 0.20371 2.08014 0.40742 0.00000 0.13479 2.82606 1.00000 412.40 570.0
12 0.52899 5.40172 1.05728 0.00000 0.00000 6.98800 0.26630 70.00 1800.0
13 0.52890 0.32791 1.00420 0.00000 0.00000 1.86100 1.00000 70.00 180.0
14 0.00000 5.07368 0.05332 0.00000 0.00000 5.12700 0.00000 70.00 180.0

110
100
90
Conversion & yield (%)

80
70
60
50
40
30 O2 yield SO2 yield H2SO4 Conversion
20
10
450 550 650 750 850 950 1050 1150 1250
Temperature (°C)

Fig. 4. Temperature stability of revised flowsheet I.

642 C. Huang, A. T-Raissi / Solar Energy 78 (2005) 632–646

are given in Table 8 as a function of acid decomposi-
tion temperatures in the range of 500–1200
C. As in
Table 3 (Bilgen’s flowsheet), if we assume that heat
released in condensers E1 and CE1 are 100% recover-
able, the total heat transfer required for the process is
very close to that calculated for the Bilgen’s flowsheet––
about 74.5% at a decomposition temperature of 850
C.
Because of high temperature (138
C) and high rate of
flow (6.998 mol/h) in the condenser E1 and stream 3, a
higher percentage of heat recovery may be possible. If
we assume zero heat loss for the heat exchanger, then,
HYSYS calculates heat recovery in stream 3 to be 100%
efficient. Since the flowsheet for S–I cycle contains
many unit operations and streams, it is reasonable to
assume that the heat released from E1 and CE1 can be
utilized to maximum advantage heating various cold
streams. Comparing two processes given in Figs. 1 and
3, we note that the higher heating energy requirement
in the improved process I is a major part of the total
heat input. The overall efficiency of the process is af-
fected by the extent of heat recovered. If only 50%
(instead of 100%) of the heat rejected in the condensers
recovered, the overall process efficiency drops from 39%
to 38%. Therefore, for the revised flowsheet I, the in-
creased process stability and simplicity was achieved in
the expense of added dependency of the overall process
efficiency on the extent of heat recovered. In addition,
due to the simpler overall configuration of the flowsheet
I, its capital and operating costs should be lower than
that of the Bilgen’s process. Finally, the temperature
stability of flowsheet I process has beneficial effect on
the decomposition catalyst used.
4.3. Improved alternative process (flowsheet II)
for sulfuric acid decomposition step
In comparing Bilgen’s process (Fig. 1) to flowsheet I
(Fig. 3), it is seen that in the Bilgen’s process, water is
separated from the sulfuric acid solution by evapora-
tion. Except for the energy input to increase pressure,
there is no need for other heat input in this process. The
trade-off is that the heat flow in the original material
stream 1 is lost as waste heat. A much larger waste heat
occurs in the condenser CE1 with a heat loss of
1.87 · 105 kJ/h. The process of flowsheet I uses a large
amount of energy (E3 ¼ 4:8  105 –5.1 · 105 kJ/h) for
sulfuric acid purification. The efficiency of the process I
is dependent upon the extent of heat recovery from
condensers E1 and CE1 (5.0 · 105 kJ/h).
An alternative approach is to combine some parts of
Bilgen’s process with process I. The new proposed
flowsheet II is shown in Fig. 5. The main difference be-
tween Figs. 4 and 5 is that in the flowsheet II, water in
sulfuric acid solution is partially evaporated to increase
the concentration before sending the material stream to
a distillation column. The evaporated water is then
mixed with the stream from the distillation column and
exits as the outlet stream. Mass balance results for sev-
eral decomposition temperatures (500, 650, 750, and 850

C) are given in Tables 9–12. Sulfuric acid conversions

Table 8
Heat exchanges for the sulfuric acid decomposition section (revised process I)
Unit 500
C 550
C 600
C 650
C 700
C 750
C 850
C 950
C 1050
C 1200
C
operations
Condenser )274,200 )274,200 )274,200 )274,200 )274,200 )274,200 )274,200 )274,200 )274,200 )274,200
(E1)
Reboiler (E3) 479,600 480,900 487,400 487,300 485,100 490,100 503,500 507,600 507,700 506,700
Pump (PE1) 69 69 69 69 69 69 69 69 69 69
Pump (PE2) 114 110 105 103 101 97 89 86 86 86
Reactor (R1) 103,700 103,300 102,900 102,500 102,200 101,800 101,100 100,500 99,900 99,210
Reactor (R2) 103,700 103,300 102,900 102,500 102,200 101,800 101,100 100,500 99,900 99,210
Heater (HE) 89,580 88,910 82,870 83,300 85,810 81,210 68,490 65,070 65,500 67,190
Condenser )229,200 )229,200 )229,200 )229,200 )229,200 )229,200 )229,200 )229,200 )229,200 )229,200
(CE1)

Total heat 273,788 273,607 273,250 272,771 272,475 272,062 271,317 270,787 270,116 269,425
flow

Efficiency (1)a 75.8 75.5 75.3 75.2 75.0 74.8 74.5 74.2 74.0 73.6
(%)
Efficiency (2)a 39.5 39.3 39.2 39.1 39.0 38.9 38.7 38.5 38.3 38.1
(%)
a
Efficiencies (1) and (2) are calculated based upon: (1) complete recovery or (2) 50% recovery of heat released from
condensers E1 and CE1.
 C. Huang, A. T-Raissi / Solar Energy 78 (2005) 632–646 643

Fig. 5. Improved HYSYS simulation flowsheet II.

Table 9
Mass balance and stream composition for revised flowsheet II (sulfur trioxide decomposition temperature: 500
C)
Stream no. Composition mole flow (kmol/h) Mole flow Vapor Tempera- Pressure
O2 H2 O SO2 SO3 H2 SO4 (kmol/h) fraction ture (
C) (kPa)

1 0.00000 4.34370 0.00400 0.00000 1.05760 5.40530 0.0000 119.90 180.0

2 0.00000 4.34346 0.00378 0.00000 1.05776 5.40500 0.7526 74.05 8.0
3 0.00000 0.27970 0.00000 0.00000 1.05730 1.33700 0.0000 74.05 8.0
4 0.00000 0.27970 0.00000 0.00000 1.05730 1.33700 0.0000 396.50 570.0
5 0.00000 0.00682 0.00000 0.00000 1.35718 1.36400 0.0000 396.40 100.0
6 0.00000 0.00682 0.00000 0.00000 1.35718 1.36400 0.0000 396.50 1200.0
7 0.00000 0.00682 0.00000 0.00000 1.35718 1.36400 0.0000 470.00 1200.0
8 0.00000 1.06447 0.00000 1.05769 0.29984 2.42200 0.8600 281.80 1200.0
9 0.00000 1.06447 0.00000 1.05769 0.29984 2.42200 1.0000 500.00 1200.0
10 0.52882 1.06443 1.05764 0.00000 0.30012 2.95100 1.0000 500.00 1200.0
11 0.52882 1.06443 1.05764 0.00000 0.30012 2.95100 0.9479 410.20 570.0
12 0.52882 1.06443 1.05764 0.00000 0.30012 2.95100 0.9479 410.20 570.0
13 0.52895 1.33744 1.05761 0.00000 0.00000 2.92400 1.0000 120.60 450.0
14 0.52895 1.33744 1.05761 0.00000 0.00000 2.92400 0.6542 70.00 180.0
15 0.52894 0.33688 1.04718 0.00000 0.00000 1.91300 1.0000 70.00 180.0
16 0.00000 1.00028 0.01072 0.00000 0.00000 1.01100 0.0000 70.00 180.0
17 0.00000 4.06393 0.00407 0.00000 0.00000 4.06800 1.0000 74.50 8.0
18 0.00000 4.06400 0.00400 0.00000 0.00000 4.06800 0.0000 41.55 20.0
19 0.00000 4.06400 0.00400 0.00000 0.00000 4.06800 0.0000 41.57 180.0
20 0.00000 5.06440 0.01471 0.00000 0.00000 5.07911 0.0000 47.26 180.0

and oxygen and sulfur dioxide yields for streams 1, 15
and 20 are comparable to those depicted in Fig. 4
and therefore are not given. Table 13 details the heat
balance results for all unit operations and efficien-
cies for process II flowsheet. Assuming complete heat
recovery from condensers E1 and CE1, the total process
efficiency [Efficiency (1)] ranges from 65.9% to 67.8%––
lower than those calculated for process I. This is so
because some heat flow from stream 1 is wasted in
condenser CE2 even though the extent of heat recovery
burden is reduced. Assuming a 50% heat recovery, the
calculated efficiency [Efficiency (2)] ranges from 51.7% to
53.3%, which is higher than that obtained for process I
(i.e. 38.5–39.5%).
5. Conclusions
The sulfur–iodine (S–I) thermochemical water split-
ting cycle is one of the most studied cycles for H2 pro-
duction. S–I cycle consists of four sections, one of which
involves sulfuric acid concentration and decomposition.
644 C. Huang, A. T-Raissi / Solar Energy 78 (2005) 632–646

Table 10
Mass balance and stream composition for revised flowsheet II (sulfur trioxide decomposition temperature: 650
C)
Stream no. Composition mole flow (kmol/h) Mole flow Vapor Tempera- Pressure
O2 H2 O SO2 SO3 H2 SO4 (kmol/h) fraction ture (
C) (kPa)

1 0.00000 4.34370 0.00400 0.00000 1.05760 5.40530 0.0000 119.90 180.0

2 0.00000 4.34346 0.00378 0.00000 1.05776 5.40500 0.7526 74.05 8.0
3 0.00000 0.27970 0.00000 0.00000 1.05730 1.33700 0.0000 74.05 8.0
4 0.00000 0.27970 0.00000 0.00000 1.05730 1.33700 0.0000 396.50 570.0
5 0.00000 0.00635 0.00000 0.00000 1.26266 1.26900 0.0000 396.40 100.0
6 0.00000 0.00682 0.00000 0.00000 1.35718 1.36400 0.0000 396.50 1200.0
7 0.00000 0.00682 0.00000 0.00000 1.35718 1.36400 0.0000 490.00 1200.0
8 0.00000 1.06414 0.00000 1.05785 0.20501 2.32700 0.9024 296.60 1200.0
9 0.00000 1.06414 0.00000 1.05785 0.20501 2.32700 1.0000 650.00 1200.0
10 0.52875 1.06377 1.05749 0.00000 0.20499 2.85500 1.0000 650.00 1200.0
11 0.52875 1.06377 1.05749 0.00000 0.20499 2.85500 0.9839 412.30 570.0
12 0.52875 1.06377 1.05749 0.00000 0.20499 2.85500 0.9839 412.30 570.0
13 0.52895 1.33744 1.05761 0.00000 0.00000 2.92400 1.0000 120.60 450.0
14 0.52895 1.33744 1.05761 0.00000 0.00000 2.92400 0.6542 70.00 180.0
15 0.52867 0.33670 1.04663 0.00000 0.00000 1.91200 1.0000 70.00 180.0
16 0.00000 1.00028 0.01072 0.00000 0.00000 1.01100 0.0000 70.00 180.0
17 0.00000 4.06393 0.00407 0.00000 0.00000 4.06800 1.0000 74.50 8.0
18 0.00000 4.06393 0.00407 0.00000 0.00000 4.06800 0.0000 41.55 20.0
19 0.00000 4.06393 0.00407 0.00000 0.00000 4.06800 0.0000 41.57 180.0
20 0.00000 5.06427 0.01473 0.00000 0.00000 5.07900 0.0000 47.26 180.0

Table 11
Mass balance and stream composition for revised flowsheet II (sulfur trioxide decomposition temperature: 750
C)
Stream no. Composition mole flow (kmol/h) Mole flow Vapor Tempera- Pressure
O2 H2 O SO2 SO3 H2 SO4 (kmol/h) fraction ture (
C) (kPa)

1 0.00000 4.34370 0.00400 0.00000 1.05760 5.40530 0.0000 119.90 180.0

2 0.00000 4.34346 0.00378 0.00000 1.05776 5.40500 0.7526 74.05 8.0
3 0.00000 0.27970 0.00000 0.00000 1.05730 1.33700 0.0000 74.05 8.0
4 0.00000 0.27970 0.00000 0.00000 1.05730 1.33700 0.0000 396.50 570.0
5 0.00000 0.00600 0.00000 0.00000 1.19301 1.19900 0.0000 396.50 100.0
6 0.00000 0.00600 0.00000 0.00000 1.19301 1.19900 0.0000 396.50 1200.0
7 0.00000 0.00600 0.00000 0.00000 1.19301 1.19900 0.0000 507.00 1200.0
8 0.00000 1.06348 0.00000 1.05761 0.13491 2.25600 0.9352 313.10 1200.0
9 0.00000 1.06348 0.00000 1.05761 0.13491 2.25600 1.0000 750.00 1200.0
10 0.52887 1.06359 1.05774 0.00000 0.13479 2.78500 1.0000 750.00 1200.0
11 0.52887 1.06359 1.05774 0.00000 0.13479 2.78500 1.0000 418.40 570.0
12 0.52887 1.06359 1.05774 0.00000 0.13479 2.78500 1.0000 418.40 570.0
13 0.52895 1.33744 1.05761 0.00000 0.00000 2.92400 1.0000 120.60 450.0
14 0.52895 1.33744 1.05761 0.00000 0.00000 2.92400 0.6542 70.00 180.0
15 0.52894 0.33688 1.04718 0.00000 0.00000 1.91300 1.0000 70.00 180.0
16 0.00000 1.00028 0.01072 0.00000 0.00000 1.01100 0.0000 70.00 180.0
17 0.00000 4.06393 0.00407 0.00000 0.00000 4.06800 1.0000 74.50 8.0
18 0.00000 4.06393 0.00407 0.00000 0.00000 4.06800 0.0000 41.55 20.0
19 0.00000 4.06393 0.00407 0.00000 0.00000 4.06800 0.0000 41.57 180.0
20 0.00000 5.06427 0.01473 0.00000 0.00000 5.07900 0.0000 47.26 180.0

The process for concentration and decomposition of
sulfuric acid is endothermic driven by the heat input
from a high temperature source. Analysis of the S–I
cycle in the past thirty years has mostly focused on the
utilization of nuclear power as the high temperature heat
source. Thermochemical equilibrium as well as kinetic
has shown that both the extent and rate of sulfuric acid
decomposition can be improved at very high tempera-
tures available only from solar concentrating devices.
The beneficial effect of high temperature solar heat for
decomposition of sulfuric acid in the S–I cycle is de-
scribed in this paper.
 C. Huang, A. T-Raissi / Solar Energy 78 (2005) 632–646 645

Table 12
Mass balance and stream composition for revised flowsheet II (sulfur trioxide decomposition temperature: 850
C)
Stream no. Composition mole flow (kmol/h) Mole flow Vapor Tempera- Pressure
O2 H2 O SO2 SO3 H2 SO4 (kmol/h) fraction ture (
C) (kPa)

1 0.00000 4.34370 0.00400 0.00000 1.05760 5.40530 0.0000 119.90 180.0

2 0.00000 4.34346 0.00378 0.00000 1.05776 5.40500 0.7526 74.05 8.0
3 0.00000 0.27970 0.00000 0.00000 1.05730 1.33700 0.0000 74.05 8.0
4 0.00000 0.27970 0.00000 0.00000 1.05730 1.33700 0.0000 396.50 570.0
5 0.00000 0.00556 0.00000 0.00000 1.10545 1.11100 0.0000 396.40 100.0
6 0.00000 0.00556 0.00000 0.00000 1.10545 1.11100 0.0000 396.50 1200.0
7 0.00000 0.00556 0.00000 0.00000 1.10545 1.11100 0.0000 535.00 1200.0
8 0.00000 1.06346 0.00000 1.05782 0.04772 2.16900 0.9798 353.30 1200.0
9 0.00000 1.06348 0.00000 1.05761 0.13491 2.25600 1.0000 850.00 1200.0
10 0.52861 1.06289 1.05776 0.00000 0.04774 2.69700 1.0000 850.00 1200.0
11 0.52861 1.06289 1.05776 0.00000 0.04774 2.69700 1.0000 570.00 570.0
12 0.52861 1.06289 1.05776 0.00000 0.04774 2.69700 1.0000 418.40 570.0
13 0.52895 1.33744 1.05761 0.00000 0.00000 2.92400 1.0000 120.60 450.0
14 0.52895 1.33744 1.05761 0.00000 0.00000 2.92400 0.6542 70.00 180.0
15 0.52894 0.33688 1.04718 0.00000 0.00000 1.91300 1.0000 70.00 180.0
16 0.00000 1.00028 0.01072 0.00000 0.00000 1.01100 0.0000 70.00 180.0
17 0.00000 4.06393 0.00407 0.00000 0.00000 4.06800 1.0000 74.50 8.0
18 0.00000 4.06393 0.00407 0.00000 0.00000 4.06800 0.0000 41.55 20.0
19 0.00000 4.06393 0.00407 0.00000 0.00000 4.06800 0.0000 41.57 180.0
20 0.00000 5.06427 0.01473 0.00000 0.00000 5.07900 0.0000 47.26 180.0

Table 13
Heat exchanges for the sulfuric acid decomposition section (revised process II)
Unit Heat or energy flow (kJ/h)
operations 500
C 550
C 600
C 650
C 700
C 750
C 850
C 950
C 1050
C 1200
C
Condenser )118,600 )118,600 )118,600 )118,600 )118,600 )118,600 )118,600 )118,600 )118,600 )118,600
(E1)
Reboiler (E3) 182,900 180,600 181,600 181,500 184,500 184,300 195,500 196,900 197,900 200,900
Pump (PE1) 45 45 45 45 45 45 45 45 45 45
Pump (PE2) 111 109 106 103 99 97 90 87 86 86
Pump (PE3) 16 16 16 16 16 16 16 16 16 16
Reactor (R1) 103,600 103,300 102,900 102,500 102,100 101,800 101,100 100,500 99,900 99,210
Reactor (R2) 103,600 103,300 102,900 102,500 102,100 101,800 101,100 100,500 99,900 99,210
Heater (HE) 80,780 83,470 82,860 83,300 80,730 81,220 70,710 69,930 69,540 67,180
Condenser )47,110 )47,110 )47,110 )47,110 )47,100 )47,110 )47,100 )47,110 )47,110 )47,110
(CE1)
Condenser )179,800 )179,799 )179,798 )179,797 )179,796 )179,795 )179,794 )179,793 )179,792 )179,791
(CE2)

Total heat 305,740 305,523 305,104 304,582 304,210 303,882 303,159 302,559 301,965 301,225
flow
Efficiency (1)a 67.8 67.6 67.5 67.3 67.1 67.0 66.7 66.4 66.2 65.9
(%)
Efficiency (2)a 53.3 53.2 53.1 52.9 52.8 52.6 52.4 52.2 51.9 51.7
(%)
a
Efficiencies (1) and (2) are calculated based on: (1) heat released from condensers E1 and CE1 can be completely or
(2) 50% recovered.

Three process flowsheets including Bilgen’s, and two and sulfur dioxide that constitute Section II in the sul-
improved versions were analyzed using the HYSYS CPS fur–iodine thermochemical water splitting cycle. Our
platform for decomposition of sulfuric acid into oxygen conclusions are summarized below:
646 C. Huang, A. T-Raissi / Solar Energy 78 (2005) 632–646
Bilgen’s flowsheet provides a highly efficient ap-
proach for decomposing sulfuric acid with a thermal
efficiency of about 77%. The disadvantages of Bilgen’s
flowsheet is its apparent complexity resulting in poten-
tially higher capital and operating costs. In addition, the
temperature stability of the Bilgen’s process is low at
reaction temperatures below 750
C. We have devised an
improved process (flowsheet I) that is simple and stable
at acid decomposition temperatures down to 500
C, yet
offers process efficiencies comparable to that of Bilgen’s
flowsheet. The overall efficiencies of the process I mod-
ification depend on the extent of heat recovery in con-
densers. An alternative process (flowsheet II) combines
these two processes (Bilgen’s and process I) with an
intermediate heat input for water separation that re-
duces the process dependence on the extent of heat
recovery in the condensers. The temperature stability of
process II is better than Bilgen’s flowsheet but has a
somewhat lower overall efficiency compared to the
above two processes. The revised flowsheets I and II
present better processes to couple with the inherently
transient heat sources such as solar energy.
Acknowledgements
The authors gratefully acknowledge the financial
support from the US Department of Energy under
Contract #DEFC3600GO10603 and NASA-GRC
under Grant NAG3-2751.
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