Energy Convers, Mgmt Vol. 36, No. 1, pp.

I 1-21, 1995
~ Pergamon Copyright~ 1995ElsevierScienceLtd
0196-8904(94)00036-0 Printed in Great Britain.All rights reserved
0196-8904/95 $9.50+ 0.00

AN IMPROVED PROCESS FOR H2SO4 DECOMPOSITION

STEP OF THE SULFUR-IODINE CYCLE

I. T. OZT~RK, A. HAMMACHE and E. BILGEN?

Mechanical Engineering Department, Ecole Polytechnique, University of Montreal, P.O. Box 6079.
St, A, Montreal, Quebec, Canada H3C 3A7

(Received 3 December 1993; received for publication 7 September 1994)

Abstract--This study presents a new design, and thermodynamic and engineering analyses of the H2SO4
decomposition section (Section II of the GA sulfur-iodine process flow sheet) of the thermochemical
hydrogen producing cycle. Thermodynamic (energy and exergy) and cost analyses have been carried out
using thermodynamic data and costs in the literature. The results show that energetic and exergetic
efficiencies are 76.0 and 75.6%, respectively, and the typical cost is 2.25 (1990) per kmol SO2 for 45
(1990)/GJ nuclear heat cost.

Sulfur iodine cycle Hydrogenproduction Sulfuricacid decomposition

INTRODUCTION
Several thermochemical cycles for water splitting using high temperature thermal energy are based
on the sulfur family processes [1-3] where the high temperature thermal decomposition of sulfuric
acid into sulfur dioxide, water, and oxygen is a c o m m o n reaction. The product sulfur dioxide is
reacted with water to produce hydrogen and sulfuric acid using either several thermochemical
steps [1] or an electrochemical step [2, 3].
One of these thermochemical cycles for water splitting using high temperature thermal energy
is the sulfur-iodine cycle. Recently, the J A E R I (Japanese Atomic Energy Research Institute) has
also chosen the sulfur-iodine cycle as one of the leading candidates in their thermochemical
hydrogen production program. Consequently, the theoretical and experimental studies have
continued and bench scale studies have been carried out to verify various steps of the cycle with
the latest development and innovations.
Theoretically, the thermochemical cycle is accomplished in three steps:

2H 2O(1) + SO2 (g) + I2 ( c ) ~ H2 SO4(aq) + 2HI(aq) (1)

2HI(aq) ~ H2(g) + I2(c) (2)

H2 SO4(1) ---*H20(l) + SO2(g) + 0.502(g). (3)

In the flow sheet developed by G A Enterprises Inc., Calif. (hereafter referred to as GA flow
sheet), equation (1) is carried out in Section I, equation (2) in Sections III and IV and equation
(3) in Section II (see Fig. 1). A brief description of the cycle is given below:
Section I is the HzSO4-HI production and separation and the 02 separation step. Recycled 12
from Sections III and IV reacts with water and SO2 in a countercurrent reactor with a mixture of
gaseous SO2-O 2. It results in formation of a solution of two acids, H2SO 4 and HI. This solution
contains two phases, the lower density phase, which contains all the H2SO4 acid at a concentration
of about 50% by weight with traces of 12 and SO2, and the higher density phase, which contains
all the H I with considerable amounts of I2 in an H 2 0 solution. Both phases are separated and the
concentration of H 2SO 4 is increased to 57% by weight by reacting the H 2SO4 phase with molten

+To whom all correspondence should be addressed.

11
12 OZTORK et al.: H2SO 4 DECOMPOSITION STEP OF SULFUR-IODINE CYCLE

II I~ 1"4H2SO4 I II
H2S04 I 0.6H20 [ H2S04
DECOMPOSER 0.4 H2SO4 r I CONCENTRATOR

4.1 H20
o4H20'SO2'0502 _1 I
, 2 HI ,12.212wl ACIDPRODUCTION
III ]'~ ] ANDSEPARATION
HI 1 10"2H20 1 W I T H 0 2 -~0"502
CONCENTRATOR] -I PURIFICATION
112.212,10.3H20I

2.1 HI 12 0.9 H20

I,v
HI
vl DECOMPOSER I ~ H20

H2, 0.1HI 0.1H20

l'v
0.1 H20,0.1 HI
-I H2PURIFICATION H2

Fig. I. GA flow sheet of sulfur-iodine thermochemical cycle for hydrogen production.

iodine and SO2. The 57% by weight sulfuric acid is then transferred to Section II for concentration
and decomposition. The lower phase containing HI, H20, I2 and SO2 goes through a degassing
step, which removes practically all the SO2 and is then transferred to Section III for purification
and HI separation. As the mixture SO2--O2, coming directly from the SO3 decomposition reaction
of Section II, passes through the reactor, the SO2 is removed by reaction with I s and H 2 0 and
the gas leaving the top of the main solution reactor is practically pure oxygen with small amounts
of iodine. The iodine is removed in a scrub column and pure oxygen leaves the system as a
product.
Section II is the HESO 4 concentration and decomposition step. The 57% by weight sulfuric acid
is concentrated in a series of flash evaporators. It is then decomposed to HsO and SO3, and the
SO3 is decomposed to SO2 and 02 at 1120 K and 0.86 MPa using high temperature nuclear heat [1].
The gaseous mixture of SOs and 02 is then separated from the Hs O and unreacted H 2SO4 before
it is sent to Section I.
Section III is the HI separation step. The HI is separated from the HI-I2-HsO solution coming
from Section I. The solution is treated with concentrated phosphoric acid, in which 95% of the
I2 is separated from the solution. The solution containing HI, HsO, HaPO 4 and some Is is
transferred to an extractive distillation column, where most of the HsO remains with the
phosphoric acid, and HI, I s and a very small amount of HsO are removed as overhead vapor. The
vapor is then cooled to condense and separate. The HI is purified to a level where it can be sent
to Section IV for decomposition after compression to 5 MPa.
Section IV is the HI decomposition step. Purified liquid HI at 5 MPa from Section III is
catalytically decomposed at 393 K in a decomposition reactor. The hydrogen product is separated
from most of the I2 and some HI in a liquid gas separator. The gaseous H2 product is then scrubbed
with HsO, and pure hydrogen is the resulting product. The Is is returned to the main solution
reaction in Section I.
Section II of the cycle is the most complicated and technologically demanding part and has been
subject to many modifications and innovations. In various studies, Section II was modified and
improved over the years. In the last version of the GA process flow sheet, Section II is mainly
 ijZTtiRK el al.: H:SO, DECOMPOSITION STEP OF SULFUR-IODINE CYCLE 13

composed of a multistage acid concentration step, an acid evaporation step and a SO-, decompo-
sition step. The internal heat matching is done by means of vapor compression. The energy
efficiency is achieved by an expensive process, which is composed of mainly shell and tube heat
exchangers. In another study, a modified process was developed to overcome the difficulties
concerning the thermodynamic and engineering problems [4]. The new design was similar to that
of the original, but it incorporated a mechanical power generating subsection for heat recovery
where 9.0 kJ electrical energy/m01 SO, is produced. Further, it was shown that the exergy losses
in various steps and the cost could be reduced considerably. This process has also been incorporated
in the latest flow sheet by the JAERI.
Clearly, there is much room for thermodynamic and engineering improvements of the sulfuric
acid decomposition section. Among the possible improvements, using adiabatic equipment, better
heat matching and reducing the mechanical power generation within Section II can be mentioned.
In the following sections, the description of a new process, which is developed based on these
points, is presented. Its thermodynamic and engineering evaluations are carried out by using exergy
and engineering methodologies.

DESCRIPTIONS OF THE PROCESS

The general flow sheet of the process is shown in Fig. 2. Various subsections can be identified:
(A) sulfuric acid concentration subsection; (B) acid evaporation and SO, production subsection;
(C) SO, decomposition subsection. The main characteristics of the thermochemical process
(subsections A-C) are that all the equipment is operated adiabatically, the sulfuric acid evaporation
and SO, production subsection operates at 1.2 MPa; also the SO, decomposition subsection
operates at 1.2 MPa, and the acid concentration subsection operates between 0.008 and 1.2 MPa.
Separately, this section has power production and vapor compression steps for recovering
maximum energy.
Parametric analyses were carried out for the SO, and SO1 productions at various conditions. The
SO, production is achieved between streams 15 and 17. By keeping the H,O and H,SO, constant
in stream 15, the equilibrium composition in stream 17 was calculated at various temperatures and
pressures. The results are presented in Fig. 3. It can be seen that the SO3 production increases
sharply with increasing temperature at the lower end of the temperature and tapers off at the higher
end. As expected, for a given temperature, the higher the pressure, the lower the SO, production.

TO SECTION I

HELIUM HEATED

__
SECTION I
N2

Fig. 2. Flow sheet of the process Section II of sulfur-iodine cycle for SO? production
14 OZT1DRK et al.: H, SO4 DECOMPOSITION STEP OF SULFUR-IODINE CYCLE

HO = 0.7637 tool
1.s H SO = I.r892 m o l ~
~, ~ P (MPa)

i 1 1.2

8°
0.5

0 ~ J I ~ I
700 800 900 1000
TEMPERATURE, K

Fig. 3. Parametric study of SO 3 production as a function of temperature.

The maximum operating pressure was determined by simulation of the entire process by taking
pressure as a parameter. This determination was based on the steam pressure in stream 13 in such
a way that all its energy could be recuperated in HX2 and HX 1 by condensing it. The temperature
of stream 17 was determined to be 800 K, based on the heat exchange between the He stream and
decomposition reactor D, then the heat exchanger HX4.
The SO2 production is done between streams 17 and 18. By taking the temperature of stream
18 as base and assuming the H 2 0 content in stream 15 equal to 0.7637mol and constant, the
equilibrium composition in stream 18 was calculated at various pressures and for various H 2SO4
and H 2 0 contents. The results are presented in Fig. 4. It is seen that, as expected, the SO2
production increases with the H2 SO4 content for a given pressure and it decreases with increasing
pressure.
The mass balance, phase, pressure and temperature in various streams are presented in Table 1
for all subsections. The description of each subsection is given below. (See Fig. 2 and Table I.)

A c i d concentration subsection
The sulfuric acid with 57% by weight concentration flowing out from Section I is circulated
through EV1, S1, HX1, $2, PI, HX2, $3 and P2 into the SO3 absorption tower T. Stream 1 is at
0.18 MPa; it is expanded at EV1 to 0.008 MPa, hence, the evaporation of some water and its
separation is achieved in SI. The biggest portion of the evaporation of water and its separation
is achieved by heating through HX1, HX2 and $2, $3. The pressure of stream 7 is increased by
pump P1 to 0.02 MPa, which is the operating pressure of HX2 and HX5. The outlet gases stream

1.8 Tout = 1120 K P (MPa)

~: 1.6
z
O 1.4 .°'" 2.0
I~ 1.2

~0.8 :.:.;:.:..........
0.6
1.5 2 2.5
H2 SO, (mol)

Fig. 4. Parametric study of SO2 production as a function of H2SO 4 content.

 OZT~RK et al.: HzSO4 DECOMPOSITION STEP OF SULFUR-IODINE CYCLE 15

Table 1. Mass balance and stream composition for 1 mol SO2 production
Stream 02 SO2 SO3 H20 H2SO 4 State T(K) P(MPa)
1 0.0040 4.3437 1.0576 1 393,0 0.180
2 0.0040 4.3437 1.0576 g/l 347.2 0.008
3 0.0035 0.3751 g 347.2 0.008
4 0.0005 3.9686 1.0576 1 347.2 0.008
5 3.9686 1.0576 g/l 367.5 0.008
6 0.0005 1.3146 g 367.5 0.008
7 2.6540 1.0576 1 367.5 0.008
8 2.6540 1.0576 1 367.5 0.020
9 2.6540 1.0576 g/l 425.7 0.020
10 1.1569 0.0017 g 425.7 0.020
11 1.4971 1.0559 1 425.7 0.020
12 1.4971 1.0559 1 425.7 1.200
13 0.5000 1.0000 2.4970 0.0559 g 445.7 1.200
15 0.7637 1.7692 1 638.2 1.200
16 0.3587 1.1223 1.4105 g/l 707.8 1.200
17 1.2813 2,0449 0.4879 g 800.0 1.200
18 0.5000 1.0000 0.7621 2.5257 0.0071 g 1120.0 1.200
19 0.5000 1.0000 0.1808 1.9444 0.5884 g 693.6 1.200
20 l. 1569 0.0017 g 370.0 0.020
21 0.3522 0.0005 g 370.0 0.020
22 0.8047 0.0012 g 370.0 0.020
23 0.8047 0.0012 g 540.7 0.080
24 0.8047 0.0012 g 420.1 0.080
25 0.8047 0.0012 1 366.7 0.080
26 0.8047 0.0012 1 366.7 0.570
27 0.5000 1.0000 2.4970 0.0559 g/1 419.4 1.200
28 0.0435 1.6600 0.0559 1 419.4 1.200
29 0.5000 0.9565 0.8370 g 419.4 1.200
30 0.5000 0.9565 0.8370 g/l 366.2 1.200
31 0.0277 0.7370 1 366.2 1.200
32 0.5000 0.9288 0.1000 g 366.2 1.200
33 0.5000 0.9288 0.1000 g 465.5 1.200
34 0.5000 0.9288 0.1000 g 338.6 0.200
35 0.5000 0.9288 o. 1000 g 376.8 0.200
36 0.0040 1.6897 g 362.9 0.008
37 0.0040 1.6897 1 314.7 0.008
38 0.0040 1.6897 1 314.7 0.570
39 0.3522 0.0005 1 333.8 0.020
40 0.3522 0.0005 1 333.8 0.570
41 0.0277 0.7370 1 366.2 0.570
42 0.0277 1.0892 0.0005 1 356.0 0.570
43 0.0317 2.7789 0.0005 1 331.0 0.570
44 0.0435 1.6600 0.0559 1 399.5 1.200
45 0.0435 1.6600 0.0559 1 399.5 0.570
46 0.0435 2.4647 0.0571 1 389.3 0.570
47 0.0752 5.2436 0.0576 1 358.7 0.570

10 f r o m $3 is c o o l e d d o w n f r o m 425.7 to 370 K in H X 5 . Th e outlet stream f r o m H X 5 is then divided

into t wo streams, 21 a n d 22, in such a way as to recuperate e n o u g h energy to use in heat exchangers
H X 6 an d H X I . S t r e a m 21 is c o n d e n s e d t h r o u g h c o n d e n s e r C2, p u m p e d t h r o u g h P6 and sent to
Section I; its energy is wasted. T o increase the quality o f the steam in stream 22, it is c o m p r e s s e d
to 0.08 M P a t h r o u g h c o m p r e s s o r Co. Its energy is then r eco v er ed in heat exchangers H X 6 an d
H X I . It is c o n d e n s e d in the latter, p u m p e d t h r o u g h P4 an d sent to Section I.
T h e pressure o f stream 11 is increased to 1.2 M P a by p u m p P2, which is the o p e r a t i n g pressure
o f the t o w e r T and o t h e r subsections. S t r e a m 12 flows in a c o u n t e r cu r r en t m o d e with i n c o m i n g
stream 19 f r o m the acid e v a p o r a t i o n subsection. S t r e a m 19 is c o o l e d in direct c o n t a c t with the cold
sulfuric acid, during which all gaseous H 2 S O 4 condenses an d the SO3 is absorbed. Liquid H2SO4
c o m i n g f r o m the b o t t o m o f t o w e r T is p u m p e d t h r o u g h P3 to the acid e v a p o r a t i o n section. A t the
end o f this subsection, the c o n c e n t r a t i o n o f the sulfuric acid in stream 15 b e c o m e s 92.7% by weight.

Acid evaporation subsection

S t r e a m 15 c o n t a i n s all liquid p r o d u c t s which are transferred to the acid e v a p o r a t i o n subsection.
It is heated f r o m 638.2 to 707.8 K, hence partial e v a p o r a t i o n o f the sulfuric acid an d partial

ECM 36 [ B
16 OZTORK et al.: H2SO 4 DECOMPOSITION STEP OF SULFUR-IODINE CYCLE

production of SO3 are done in HX3. The mixture of gas and liquid is then circulated through HX4
where all sulfuric acid is evaporated, and the SO3 production is achieved at 800 K. Nuclear heat
is used in HX4 at a lower temperature level, by the He vector. The outgoing gaseous stream 17
from HX4 is sent to the SO 3 decomposition subsection.

S03 decomposition subsection

The gaseous products in stream 17 are sent to the decomposition reactor D where the SO3 is
catalytically decomposed at 1120 K. The high temperature nuclear energy is supplied by the He
vector. The outlet gases in stream 18 from the decomposition reactor D is sent to heat exchanger
HX3, where it is cooled to 693.6 K before entering the absorption tower T. The SO3 is completely
absorbed in tower T, and the product SO2, together with other gases, comes out in stream 13. The
outlet gases in stream 13, containing 1 mol SO2, are finally cooled to the condensing temperature
of the water in heat exchangers HX2, HX 1, and separated in $4 and $5. Stream 32 contains 0.5 mol
02, 0.9288 mol SO2 and 0.1 mol H20 at 366.2 K and 1.2 MPa. Stream 32 is heated to 465.5 K in
HX6 then expanded to 0.2 MPa through expander EXP. Outgoing stream 34 from expander EXP
is heated to 376.8 K in HX5 before going into Section I.

THERMODYNAMIC EVALUATION
The decomposition process consists of various modules and streams where chemical reactions
involving composition, temperature and pressure changes take place. The first and second laws of
thermodynamics, for an open and steady flow system, can be written for each module as
Qm -- Wm = AH (4)

aH = E n~ - E'H (5)
out in

Qm
Sm= AS - - - (6)
To

AS = Z nS - Z nS. (7)
OUt in

Using equation (4) and (6), the entropy production in a module S,, can be calculated as
Wm+AH
sm= A s (8)
To
The exergy loss in the mth module is calculated from the Gouy-Stodola theorem and defined as
Em= ToSm. (9)
The total exergy loss of the process is obtained by summation of all the exergy losses for each
module.
Eros, = ZmEm. (10)
The overall thermal efficiency (or the first law efficiency) of the process is calculated as

Q.~.,,,,o. (ll)
tI = ZQ i

where Q,e,,,io, is the overall reaction between (stream 1 ) ~ (streams 35, 47) and ZQ~ is the total
thermal energy supplied to the process, including the thermal energy equivalent of the needed
electrical energy, if any.
The overall exergetic efficiency of the process is calculated as
greaction
c -- - - (12)

where E,¢,,,.,~o,is the exergy difference between (stream 1)---* (streams 35, 47), and ELi is the total
exergy supplied to the process.
 OZTORK et al.: H~S04 DECOMPOSITION STEP OF SULFUR-IODINE CYCLE 17

Thermodynamic models and codes

The thermodynamic evaluation of the processes shown in Fig. 2 has been carried out using a
computer code developed at the Ecole Polytechnique. The code has a main program connected to
various models and a thermodynamic data bank. The major models are for chemical equilibrium
composition calculations, thermodynamic calculations of reactions with known compositions and
power equipment. The thermodynamic (energy and exergy) analyses have been carried out based
on the data in the literature (Thermodynamic Data Bank by Telus-NASA Lewis-Ecole Polytech-
nique) and thermodynamic properties of sulfur compounds [5]. The assumptions for the single and
mixture phases were: (i) all single phase gases were considered ideal, all liquid phases of H20(1)
and HzSO4(l) as real; (ii) all mixture phases were considered as ideal and the H20-H2SO 4 liquid
phase as real; (iii) Henry's law was used for the mixture of H20(l) and SO2. In the latter case, the
thermodynamic properties were taken from Ref. [5]. For the exergy analysis of the cycle, the
temperature and pressure of the dead state were taken as 298.15 K and 1 atm. Sulfur components,
such as SO2, SO3, H2SO4, were reacted with CaCO3 and water in the atmosphere[6]. Their
concentration in the atmosphere was taken as reference for H20, CO2 and Oz. The details of the
thermodynamic codes have been presented elsewhere [7].

ENGINEERING EVALUATION
Engineering models and codes
The engineering evaluation code contains the routines Cost and Econ to calculate cost and
economics. Cost is a modular estimating routine based on standard chemical engineering costing
techniques[8-10]. Cost produces the total installed equipment cost Ct. Econ evaluates the
economics and calculates the levelized cost of the product, which is the average cost during the
operation period. It is calculated by integrating all costs over the operation period and dividing
the results by the year of operation. The details of the engineering codes have been presented
elsewhere [7].

Plant size
With reference to [11], the plant capacity is taken as 7.1 106 GJ hydrogen/yr. This requires
2.527 x 10l°mol of SO2 production/yr. Therefore, the engineering evaluation is based on this
capacity.

Materials
The materials used are divided into three main classes (see Ref. [12], for details). Depending on
the aggressiveness, temperature level of the fluids and equipment, three classes of material are
selected. For the liquid phase and liquid-vapor phase at low and medium high temperatures in all
direct contact reactors, columns and piping, carbon steel is used. For heat exchangers at low
temperatures up to 650 K, stainless steel AISI 310 or 316 for corrosive fluids and carbon steel for
non-corrosive fluids are used. For heat exchangers at high temperatures, Incoloy 800 is used for
the gas phase and titanium for the liquid phase. For example, for the most expensive equipment
of heat exchangers, the cost levels corresponding to the three classes of material were 1 for carbon
steel, 2.5 times the cost of carbon steel for stainless steel and 4.5 times the cost of carbon steel for
the Incoloy 800. The multipliers were different for different equipment.

Economical assumptions
The methodology followed in evaluating thermochemical cycles was adopted for utility financing
with 100% debt. The construction period was 3 yr, the interest rate above inflation during
construction and operating period was 5% with 0% inflation rate (i.e. constant dollar). The initial
operating and maintenance cost was assumed to be 1% and the fixed charges as 6% of the start-up
cost. The latter was estimated as follows: 1.3% depreciation, 0.3% interim replacement, 0.2%
insurance, 2.8% state and local taxes and 1.4% property tax with no federal taxes or gross profit.
Plant service life was taken as 20 yr; however, that for the equipment operating in a corrosive
environment was assumed to be 12 yr [8].
18 OZTORK et aL: H2SO 4 DECOMPOSITION STEP OF SULFUR-IODINE CYCLE

Cost of high temperature nuclear heat

Various references quote various costs: Ref, [13] used 7.55/GJ, during the International Energy
Agency Workshop of 8-I 1 August 1989, the cost estimate by the JAERI was 3.8 ¥/100 kcal or
6$/GJ, and Ref. [14] used 3.55/GJ in 1985. When updated to $ (1990), the costs from the latter
two are between 3 and 6$/GJ heat, which is assumed in this study.

R E S U L T S A N D DISCUSSION

Thermodynamic evaluations of Section II based on the flow sheets in Refs [1, 4] and engineering
evaluation of the flow sheet in Ref. [4] were first carried out. The results, which were verified with
published results, will be used later for comparison with the results from the new design. In the
following sections, the results of the thermodynamic and engineering evaluations of the new design
will be presented in detail and discussed.

Thermodynamic evaluation
Power, energy load, energy loss, exergy loss and cost ($1990) for various equipment are
summarized in Table 2.
Table 2 shows that the available mechanical energy is 7.481 kJ/mol SO: from EXP. The work
load of compressor Co is 4.800 kJ/mol SO2. Those of pumps P1-P6 amount to 0.160 kJ/mol SO2.
Hence, the total power required is 4.960 kJ/mol SO2, and the excess power which can be used in
the cycle is 2.521 kJ/mol SO:. Assuming a 40% conversion efficiency, the primary energy
corresponding to the excess power is 6.303 kJ/mol SO:. The primary energy used in the
decomposition reactor D and heat exchanger HX4 for the decomposition process amounts of
373.050 kJ/mol SO2. Therefore, the net primary energy use is 366.747 kJ/mol SO2.
Heat matching is accomplished between heat exchangers HX6 and HX7. The heat losses from
condensers C1 and C2 are 91.563 kJ/mol SO2. The temperature levels of these rejected heats are
too low for an economical conversion, and they are wasted. It is noted also that, since most of
the equipment works adiabatically, the heat losses are zero in the major equipment.
The enthalpy balance is verified by calculating the enthalpy change in the process. The enthalpy
change between stream 1 and streams 35, 47 is 278.643 kJ/mol SO2, the excess power output was
found as 2.521, and the rejected heats were 91.563 kJ/mol SO:, giving a total of 372.727 kJ/mol
SO2. The heat input was determined as 373.050 kJ/mol SO2 nuclear heat for decomposition. Thus,

Table 2. Power, energy loads, exergy losses and costs (19905) for l mol SO,
production
Unit Description W(kJ) Q (kJ) E(kJ) C(M$)
D SO 3 Decomp. reactor 0.000 222.443 9.456 16.4
T Tower 0.000 96.600 6.221 4.4
HX1 Heat exchanger 0.000 69.685 5.211 2.2
HX2 Heat exchanger 0.000 77.128 7.572 1.7
HX3 Heat exchanger 0.000 158.198 14.326 8.3
HX4 Heat exchanger 0.000 150.607 8.260 13.3
HX5 Heat exchanger 0.000 2.216 0.163 0.3
HX6 Heat exchanger 0.000 5.903 0.286 0.9
HX7 Heat exchanger 0.000 2.518 HX6t HX6t
COM Compressor 4.800 0.000 0.406 3.8
EXP Turbine - 7.481 0.000 1.207 0.9
CI Condenser 0.000 76.072 2.630 1.4
C2 Condenser 0.000 15.491 1.160 0.3
PI Pump 0.001 0.000 0.000 0.0~:
P2 Pump 0.121 0.000 0.030 0.2
P3 Pump 0.000 0.000 0.000 0.1
P4 Pump 0.010 0.000 0.002 0.0:~
P5 Pump 0.023 0.000 0.006 0.0:~
P6 Pump 0.005 0.000 0.001 0.0:~
S1/$5 Separators 0.000 0.000 0.000 0.0:~
Mix and throt 0.000 0.000 2.547 0.0:~

Total -2.521 59.574 54.2

t = heat match, ~ = negligible cost.
 O Z T O R K eta/.: H2SO 4 D E C O M P O S I T I O N STEP OF S U L F U R I O D I N E CYCLE 19

the difference between these two figures is 0.323 kJ/mol SO2. This represents 0.02% error with
respect to the total enthalpy input, which is 1749.110 kJ/mol SO2.
The exergy losses in various modules are also shown in Table 2. It can be seen that the total
exergy loss is 59.574 kJ/mol SO 2. The excess power produced by the process was 2.521 kJ/mol SO2.
The total becomes 62.095 kJ/mol SO2. The exergy supplied to the process by the He stream was
determined as 256.015 k J/tool SO 2. The difference between the exergy supplied and the exergy spent
is 193.920 kJ/mol SO,, which should be the sum of the exergetic contents of the products and of
the waste heat. This last figure from the code can be verified by calculating the exergy balance in
the process. The exergy difference between stream 1 and streams 35 and 47 is calculated as
191.133 kJ/mol SO2. The exergy corresponding to the heat losses is 2.159 k J/tool SO2. The sum of
these is 193.292 kJ/mol SO2. The difference between 193.920 (generated by the code) and 193.292
is 0.628 kJ/mol SO,,. This represents 0.07% error with respect to the total exergy supply to the
process by the helium and stream 1, which amounts to 944.096 kJ/mol SO2. It can be seen that
the error from code is negligibly small.
The energy and exergy efficiencies are calculated from equation (11) and (12) Qr,,~,,o,=
278.643 kJ/mol SO2, the total thermal energy supplied to the process was determined as
366.747 kJ/mol SO2. Hence, the overall thermal efficiency is calculated as 76.0%. E,,,,,,i,,. is the sum
of 191.132 kJ/mol SO 2 and 2.521 kJ/mol SO2 (the excess power), i.e. 193.653 kJ/mol SO2. The net
exergy supplied to the process was determined as 256.015 kJ/mol SO2. Hence, the overall exergetic
efficiency is calculated as 75.6%.
Table 2 shows the equipment with high exergy losses. These are necessary exergy losses to drive
the process. Still, by optimization techniques, the exergy losses may be minimized. However, this
should be done with cost evaluation, therefore, using the engineering process flow sheet rather than
the thermodynamic one.

Engineering evaluation
A summary of the cost estimates for the various equipment is presented in Table 2. The total
cost is calculated as M$ (1990) 54.237.
Using the cost result and taking the process heat cost as variable, the sulfur dioxide production
cost is calculated, and the results are presented in Fig. 5. In these calculations, the capital charge
rate was estimated for each process based on the initial investment, salvage value and taxes,
insurance, etc. and the cost of the process heat varied from 3.0 to 6.05 per GJ. For the typical
nuclear heat cost of 45 per GJ, the cost of the SO2 is 2.25 (1990) per kmol SO2. For the limiting
case of a low cost nuclear process heat (3.05 per G J), the cost of a kmol SO2 is found to be 1.85
(1990). The cost contributions of (capital + O & M) and nuclear heat are shown separately. The
first is independent of the nuclear heat cost and constant. The sum of the two is the total cost,
which varies linearly with the nuclear heat cost.

Comparison of results
As mentioned before, the processes in Refs [1, 4] have been evaluated using the same thermodyn-
amic models. Comparative results are presented in Table 3. Various results for the intermediate

GA PROCESS ~
4

U) 3

I I I I I

3,5 4 4.5 5 5.5

$/GJ NUCLEAR HEAT

Fig. 5. Levelized cost of SO 2 as a function of nuclear heat cost and its components for a process plant
producing 2.527 x 10 I° tool SO_,/yr.
20 OZTt]RK et al.: HzSO 4 DECOMPOSITIONSTEP OF SULFUR-IODINE CYCLE

Table 3. Comparative results for three decomposition processes. Thermodynamicresults are for
I mol SO2 production, cost for 2.527 × l0 I°tool SOz/yr. The values are in kJ/mol SO2
GA process[1] Schepersprocess[4]
Area (kJ/mol SO2) This study
Acid Required heat 286.1 260.8 251.5
concentration Recoveredheat 286.1 260.8 251.5
Electr. energy 45.2 -9.0 -2.5
Exergy losses 52.5 34.3 27.4
Acid Required heat 303.0 349.7 308.8
evaporation Recovered heat 144.7 201.8 158.2
Nuclear heat 158.3 147.9 150.6
Exergy losses 28.5 25.4 22.6
SO3 Nuclear heat 188.9 263.5 222.4
decomposer Exergy losses 11.8 10.6 9.6
Section II Nuclear heat 347.2 411.4 373.0
Electr. energy 45.2 -9.0 -2.5
Total nuclear heat 460.2 388.9 366.7
Exergy losses 92.8 70.3 59.6
Section II First law eft. (%) 63.5 70.2 76.0
Second law eft. (%) 68.6 70.0 75.6
S-I cycle Hydr. prod. eft. (%) 47.0 53,2 55.5
Section II Total cost MS 146.1 58.0 54.2

steps, namely acid concentration, acid evaporation and SO3 decomposition are presented together
with the results for the whole process. It can be seen that the present flow sheet is much superior
to the other two, since the exergy losses in the intermediate steps and for the process are reduced
considerably; nuclear heat use is reduced and the first and second law efficiencies are improved.
The first law efficiency improvement is 8.3 and 19.7% with respect to those in Refs [4] and [1],
respectively. The corresponding improvements are 7.9 and 10.2% for the second law efficiency. By
assuming that the thermal performance remains the same for the other three sections of the cycle,
the first law efficiency for the hydrogen production is also calculated for the three processes. The
results show that the present flow sheet gives 4.3 and 18.1% higher efficiency with respect to the
other two flow sheets.
The last line of Table 3 shows, also, the total costs of the other two processes. The cost of the
flow sheet in Ref. [4] was estimated using the same engineering model and that of Ref. [1] was taken
from Ref. [13] and updated to $ (1990). The cost estimate of the flow sheet [4] given in Ref. [13],
when updated from $ (1983), is MS (1990) 57.7. It is seen that the difference in the two estimates
is negligible. It is seen that the investment cost of the process in this study is less than the other
two by 60.4 and 6.6%, respectively.
The costs of kmol SO: from the two other processes in Refs [1] and [4], which were evaluated
similarly, as also shown in Fig. 5. It is seen that the cost of SO2 from this study is 5.6% less than
that in [4] for the typical cost for 4.0$/GJ nuclear heat. It is 43.4% lower than that in Ref. [1] for
the same nuclear heat cost.

CONCLUSIONS

A new process has been developed to decompose sulfuric acid in the thermochemical nuclear
hydrogen producing sulfur-iodine cycle. In the new process, all major equipment is operated
adiabatically at a maximum pressure of 1.2 MPa. Thermodynamic evaluation of the process has
resulted in 76.0% first law efficiency and 75.6% exergetic efficiency. Levelized costs of a kmol SO2
are found to be from 1.85 (1990) for a nuclear energy cost of 3.05 per GJ, to 3.05 (1990) for the
nuclear energy cost of 6.005 per GJ.

REFERENCES
1. J. H. Norman, K. J. Mysels,D. R. O'Keefe, S. A. Stowell and D. G. Williamson, Proc. 2rid WHEC, Zurich, Switzerland,
pp. 513-544 (1978).
 OZTORK et al.: H2SO 4 DECOMPOSITION STEP OF SULFUR-IODINE CYCLE 21

2. G. H. Parker and P. W. T. Lu, Proc. 14th Int. Soc. Energy Conversion Engng Conf., Boston~ Mass., pp. 752-755 (1979).
3. A. Broggi, R. K. Joels, G. Mertel, M. Morbello and B. Spelta, Hydrogen Energy Prog. 4, 1929 (1980).
4. H. Schepers, Thermodynamische Analyse yon Schwefels/iurezyklen zur Wasserspaltung. Dissertation, RTWH Aachen
(1983).
5. J. Helmig, Beitrag zur Korrelation von Phasengleichgewichten. Dissertation, RWTH Aachen (1983).
6. R. A. Gaggioli and P. J. Petit, Chem. Tech., p. 469 (August 1977).
7. A. Hammache and E. Bilgen, Chem. Engng TechnoL 15, 331 (1992).
8. M. S. Peters and K. D. Timmerhaus, Plant Design and Economics for Chemical Engineers, 4th Edn. McGraw-Hill, New
York (1991).
9. K. M. Guthrie and W. R. Grace, Chem. Engng 76, 114 (1969).
10. A. Chauvel, P. Leprince, Y. Barthel, C. Raimbault and J. P. Arlie, Manual of Economic Analysis of Chemical Processes,
Feasibility Studies in Refinery and Petrochemical Processes. McGraw-Hill, New York (1981).
11. A. Hammache and E. Bilgen, Proc. 2nd Tech. Workshop, Int. Energy Agency (Edited by B. D. Struck), pp. 29--47.
Jiilich, Germany (4-6 September 1991).
12. C. Bilgen and E. Bilgen, Int. J. Hydrogen Energy 4, 241 (1986).
13. K. F. Knoch, H. Schepers and K. Hesselmann, Hydrogen Energy Prog. V 2, 487 (1984).
14. H. Barnert, On the potential of the improvement of the competitiveness of coal refinement processes by application
of HTR process heat. CEC Meeting of the Economics and Market Working Party (1985).