Huang Dan

SULFUR-IODINE THERMOCHEMICAL CYCLE FOR

HYDROGEN PRODUCTION

Bachelor Thesis

CENTRAL OSTROBOTHNIA UNIVERSITY OF APPLIED

SCIENCES

Degree Program in Chemical and Technical Engineering

June 2009
Abstract
CENTRAL OSTROBOTHNIA
UNIVERSITY OF APPLIED SCIENCES

Degree Program in Chemical and Technical Engineering

Author: Huang Dan Pages: 24

Subject: Sulfur-Iodine thermochemical cycle for hydrogen production
Supervisor: Kaj Jansson

The aim of the thesis was to study the Sulfur-Iodine thermochemical cycle for hydrogen
production. There were three reactions in this cycle: Bunsen reaction, sulfuric acid
decomposition and the hydriodic acid decomposition. The sulfuric acid decomposition
required most heat in these three reactions. The thermal efficiency of this cycle mostly
affects this section. The HYSYS simulator by Aspen Technologies was used for sulfuric
acid decomposition. There were two steps in this section: sulfuric acid concentration and
sulfuric acid decomposition. Thus two separate HYSYS simulations, firstly, were built for
each of them. Then a whole process simulation was made for analysis. Based on the
HYSYS analyses and the statistic of this data, 650C was found the most suitable
temperature for sulfuric acid decomposition with the highest thermal efficiency of 75.11%.

Key words: Sulfur-Iodine cycle, sulfuric acid decomposition, HYSYS simulation

CONTENT:

1 INTRODUCTION..1
1.1 Background.....1
1.2 Purpose and Goals of the project...2
2 THE SULFUR-IODINE THERMOCHEMICL WATER-SPLITTING CYCLE.4
2.1 Thermochemical water-splitting cycle....4
2.2 Inventing and Development of the S-I Cycle process....4
2.3 Process description...5
2.3.1 Three main chemical reaction equations in S-I cycle...5
2.3.2 Description for those three sections...6
2.4 Advantages and Disadvantages of S-I Cycle..8
3 HYSYS SIMULATION FOR SULFURIC ACID DECOMPOSITION..10
3.1 Introduction10
3.2 HYSYS simulation code.10
3.3 Description of the simulation11
3.3.1 H2SO4 concentration.11
3.3.2 H2SO4 decomposition13
3.3.3 The whole process simulation.14
4 RESULTS AND DISCUSSION.....17
4.1 The workbook of the HYSYS simulation.17
4.2 Mass balance of the process...18
4.3 Energy requirement and efficiency...20
5 CONCLUSION.22
6 REFERENCES..23
 1

1 INTRODUCTION

1.1 Background

Energy is always the hot topic around the world. There are many different forms of energy
carriers: the solid (e.g. wood, coal), the liquid (e.g. petrol, alcohol) and the gas (e.g. nature
gas). For an energy carrier to enter the market, several objectives should be considered.
The first one is the efficiency of the energy getting from burning those energy carriers: It is
easy to see that the gas should be the most efficient energy carrier. When the distance
between the molecules in gas form is the longest and well touched with oxygen, thus gas
form burns much better the other two forms (solid and liquid) and gets more efficiency.
Moreover the transportation of gas form energy carrier is the easiest one by using the
pipelines. From these two objectives, gas form energy carriers should be the best in those
three forms. Therefore the applications worldwide are slowly shifting from the solid energy
carrier to gas form. Moreover another important objective that should be considered is the
pollution. Carbon not well burned gets the toxic gas CO. Burning wood and coal it is easily
to form CO. But even when well burned they still gets CO2, cause of global warming. Thus
new energy carriers are needed for the market. For a new energy carrier to enter the market,
those objectives must be met. Today hydrogen (H2) is one of the most widely used new
energy sources, and as it is a non-pollution and reproducible gas-form energy carrier, the
only product from burning it is water. International cooperation aims at delivering H2 as a
replacement fuel for vehicles. Hydrogen will be used as fuel for transport vehicles instead
of gasoline/diesel oil/natural gas as fuel step by step in the future. The worldwide demand
for hydrogen is about 50 million tons per year, and it is growing rapidly. Many experts
believe that hydrogen will overtake electricity as the preferred energy source. (Thomas
2007.)

There are many ways to produce hydrogen, but not all of the methods can be a compromise
between hydrogen economy and safety of environmental. The thermochemical method to
produce hydrogen shows a big potential for hydrogen economy. In this method, high
temperature heat is used as energy input to a sulfur-iodine water splitting cycle to get
hydrogen. The sulfur-iodine cycle process, invented at General Atomics Company in the
1970s, is one such cycle developed for the large scale hydrogen production. The only input
 2

in this cycle is water and the only products are hydrogen and oxygen. Unlike electrolysis,
thermochemical cycles for splitting water can convert thermal energy directly into
chemical energy by forming hydrogen and oxygen, without any greenhouse gas product.
(Huang & T-Raissi 2005, 632.)

The sulfur iodine (S-I) water splitting cycle for hydrogen production consists of three
coupled chemical reactions. The first reaction is called the Bunsen reaction. The second
reaction is the HI decomposition reaction. The third reaction is the sulfuric acid
decomposition reaction. In the S-I cycle, most of the input heat goes into the dissociation
of sulfuric acid. The next reaction is the decomposition of water into hydrogen and oxygen.
The whole process takes only water and high temperature heat and releases only hydrogen,
oxygen and low temperature heat. All reagents are recycled; there are literally no effluents.
The S-I cycle does require high temperatures, but offers the prospects for high efficiency
conversion of heat energy to hydrogen energy. As the S-I cycle is widely used around the
world today, more and more scientists pay attention on this topic. They try to decrease the
heat energy used in the cycle and to make the process more efficient. (Patel, Maheshwari,
Vijayan & Sinha 2005.)

1.2 Purpose and goals of the project

The purpose of this thesis is to study the S-I cycle flowsheet, the heat transfer in the cycle
and the efficiency of the process. The reaction that requires the greatest heat input is the
thermal decomposition of H2SO4, typically at temperatures in the range of 800-900C.
Higher temperatures tend to favor greater efficiency. If the high temperature can be
decreased to some extent, yet keeping efficiency in the same level, or even higher, then a
great deal of sources can be saved. Thus H2SO4 decomposition is considered as the most
potential step for making the process more efficient and for saving energy.

In this thesis the HYSYS chemical process simulator by Aspen Technologies is used for
analyzing and increasing the sulfuric acid (H2SO4) decomposition efficiency in order to
find a new solution for increasing the whole process efficiency. Also the HYSYS
simulation based on the Bilgen flowsheet will be the most important aim for this thesis.
After constructiong the simulation, five different temperatures of 650C, 700C, 750C,
 3

800C and 850C will be used for analyzing for the decomposition of sulfuric acid
(H2SO4). A suitable temperature for sulfuric acid decomposition with the high efficiency
should be found in this thesis. The temperature stability of the Bilgen flowsheet is low. An
effort will be made to achieve higher temperature stability in this simulation.
 4

2 THE SULFUR-IODINE THERMOCHEMICL WATER-SPLITTING CYCLE

2.1 Thermochemical water-splitting cycle

Thermochemical production of hydrogen involves the separation of water into hydrogen

and oxygen through chemical reactions at high temperatures (450-1000C), and all the
other chemicals are recycled in the process (Brown 2007a):

AO + H2O AO2 + H2
AO2 + BO ABO2 + 1/2 O2
ABO2 AO +BO

H2O H2 + 1/2 O2

A thermochemical water-splitting cycle involves a series of chemical reactions, some at

higher temperatures than others. Engineers carefully choose chemicals to create a closed
loop system that reacts with water to release oxygen and hydrogen gases. All reactants and
compounds are regenerated and recycled. Studies conducted through the Nuclear Energy
Research Initiative were identified more than 100 different thermochemical water-splitting
cycles. A few of the most promising cycles were selected for further research and
development based on the simplicity of the cycle, the efficiency of the process and the
ability to separate a pure hydrogen product. (Hydrogen 2008.)

The biggest challenge with thermochemical processes today is corrosion of process

reactors and system materials. The reaction that requires the greatest heat input is the
thermal decomposition of H2SO4, typically at about 850C. Higher temperatures tend to
favor greater efficiency. (Hydrogen 2008.)

2.2 Inventing and Development of the S-I Cycle process

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 investigated.
 5

The research collaboration of General Atomics (GA), Sandia National Laboratory (SNL)
and University of Kentucky (UK) found 115 unique thermochemical cycles, but just 25 top
thermochemical cycles selected to screening. Thermochemical cycles which have been
intensively studied include Sulfur-Iodine, UT-3 Univ. of Tokyo, Westinghouse, Ispra Mark.
The sulfur-iodine cycle for hydrogen production was invented at General Atomics (GA) in
the 1975. Moreover all steps of the process were demonstrated at GA in 1975-1986. Full
chemical flowsheets, process equipment sizing and plant cost estimates were generated for
fission, fusion and solar powered plants 1980s, 2002, 2005. (Brown 2007a; Thomas
2007.)

Extensive work was and is being carried out in other countries widely. Phase equilibrium
measurements were conducted in Germany in the 1980s. Innovative flowsheets were
developed in Canada in the 1980s and 1990s. Closed loop glass demonstration for the S-I
cycle process were invented in Japan at the early 2000s. Currently there is experimental
S-I programs in the US, France, Japan, China, Korea, India, Italy globally all over the
world. (Brown 2007a.)

2.3 Process description

2.3.1 Three main chemical reaction equations in S-I cycle

The sulfur-iodine cycle is a prime example of a thermochemical cycle. It consists of three

chemical reactions, which sum to the dissociation of water. (ztrk, Hammache & Bilgen
1995.)

Reaction equation (1) exothermic (20-120C, H = -75(15) kJ/mol)

I2 + SO2 + 2 H2O = 2 HI + H2SO4
Equation (1) is the Bunsen reaction. This is an exothermic reaction. it is spontaneous react
at 20C to 100C. At certain reactant concentrations, involving an excess of iodine, a phase
separation occurs between the two acid products leading to a H2SO4 phase principally
devoid of HI.
 6

Reaction equation (2) endothermic (600-900C, H = +186(3) kJ/mol)

2 H2SO4 = 2 H2O + 2SO2 + O2
Equation (2) is the sulfuric acid decomposition step, which can be assumed to two
reactions:
H2SO4 = SO3+ H2O (4)
2 SO3 = 2 SO2+ O2 (5)
The first stage (equation 4), occurs at a temperature of 300-400C, whereas the second
stage, given by equation (5), occurs at 600-900C with some solid catalyst.

Reaction equation (3) endothermic (300-450C, H = +12 kJ/mol)

2 HI = H2 + I2
Equation (3) is the hydriodic acid decomposition reaction. This is a slightly endothermic
reaction at the temperature 300-450C, and it can be conducted in the liquid or gas phase.

2.3.2 Description for the three sections

There are three sections in S-I cycle process. The cycle system is clearly showed in Graph
1. And it easily seen just water in and oxygen and hydrogen out.
 7

GRAPH 1. Overview of the Sulfur-Iodine process

Section I is for the Bunsen reaction, which produce and separate H2SO4 and HI for section
II and III, and the O2 is also separated in this step. Recycled I2 from Sections III reacts with
water and SO2 which comes from section II in a countercurrent reactor. They spontaneouse
reacted at 20C to 100C. It results in the formation of a solution of two acids, H2SO4 and
HI. This solution contains two phases with different density. The lower density phase
contains all the H2SO4 acid at a concentration of about 50% by weight with traces of I2 and
SO2. And the higher density phase contains all the HI with amounts of I2 in an H2O
solution and also small amount of SO2. Both phases are separated. The concentration of
H2SO4 is increased to be about 57% by weight by reacting the H2SO4 phase with molten
iodine and SO2. Then sulfuric acid with some water is transferred to Section II for
concentration and decomposition. The lower phase containing HI, H2O, 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. And for the oxygen separate. It was mixed
 8

with SO2, coming directly from the SO3 decomposition reaction of Section II, then it
passes through the reactor, the SO2 is removed by reaction with I2 and H2O, and the gas
leaving the top of the main solution reactor is practically the pure oxygen, but there is a
small amount of iodine with them. A scrub column is used for removing iodine. Then the
pure oxygen leaves the system as a product. (ztrk et al. 1995, 11.)

Section II is the H2SO4 concentration and decomposition step. The concentration is a

important part before decomposition. The 57% by weight sulfuric acid is concentrated in a
series of flash evaporators and separators. It is then decomposed to H2O and SO3, and the
SO3 is decomposed to SO2 and O2 at 850C. The nuclear energy is used in this reactor. The
gaseous mixture of SO2 and O2 is then separated from the H2O and unreacted H2SO4
before it is sent to Section I. Most heat needed in this section, as it reacts at high
temperature about 850C. (Brown 2007a.)

In Section III there are also two steps: the HI separation step and the HI decomposition
step. In the HI separation step: the HI is trying to be separated from the HI-I2-H2O solution
which comes from Section I. It is complex step as there are three compounds should be
separated from HI. In this step a concentrated phosphoric acid is used to separate 95% of
the I2 away from the solution. The solution containing HI, H2O, H2SO4 and some I2 is
transferred to an extractive distillation column, where most of the H2O remains with the
phosphoric acid, and HI, I2 and a very small amount of H2O are removed as overhead
vapor. The vapor is then cooled to condense and separate. The purified liquid HI at 5 MPa
from HI separation step is pumped into a decomposition reactor. Then it catalytically
decomposed at about 300C in it. After the reaction another separation should be taken to
get the pure hydrogen production. The hydrogen product is separated from most of the I2
and some HI in a liquid gas separator. Then the gaseous H2 product is scrubbed with H2O.
Finally, the pure hydrogen is the resulting product in this step and flow out from there. And
the I2 is returned back into Section I. (ztrk et al. 1995, 12.)

2.4 Advantages and Disadvantages of S-I Cycle

A major advantage of the S-I cycle for hydrogen production is that there are not any
harmful by products or emissions from the process. All the chemical reactions have been
 9

demonstrated. The only out let is hydrogen and oxygen. If it can be heated with a nuclear
source, it could prove to be an ideal environmental solution to hydrogen production. And
one more important advantage is that it offers the higher efficiency than any other
hydrogen production process. (Crosbier & Chapin 2003; also see Brown 2006.)

However there are some disadvantages in this cycle. There are sulfuric acid and hudroiodic
acid contained in this cycle, both of them are very corrosive, it is really harmful and must
be contained properly. The material of the reactors and all the units in this cycle should be
avoided to acid. And Iodine is an expansive material. One more thins is for the controlling
of the reaction conditions is a significant hurdle. As a lot of models are just build up from
the laboratory. It was in an idea condition for the reaction. There are coming the operation
problems. (Crosbier & Chapin 2003.)
 10

3 HYSYS SIMULATION FOR SULFURIC ACID DECOMPOSITION

3.1 Introduction

Section II (H2SO4 concentration and decomposition) needs most heat in the S-I
thermochemical water splitting cycle. Thus this section is considered the most investigated
part of the process. There is much room for thermodynamic improvement of this section. A
lot of scientists work in this section, and it is generally accepted that the efficiency of the
whole process depends on the efficiency of H2SO4 decomposition. There are lot of
possibilities for improvement, using adiabatic equipment, better heat matching and
mechanical power generation. (ztrk, el al. 1995, 12.)

A very high efficient flowsheet was published by ztrk in 1995 named Bilgens flowsheet.
It reported that thermodynamic evaluation of the process was resulted in 76% first law
efficiency and 75.6% exergetic efficiency. In this paper a HYSYS simulation was based on
this flowsheet and used its data. (ztrk, et al.1995, 12.)

In this flowsheet it can be divided into two important parts: sulfuric acid concentration and
decomposition. There are two HYSYS simulations for both of the steps in this paper. The
concentration part is very important, as the higher purity of the sulfuric acid can be
obtained before it enters to the decomposition unit, after this the higher efficiency for the
decomposition can be carried out.

3.2 HYSYS simulation code

In the HYSYS simulation for the section II both sulfuric acid concentration and the
decomposition there are five chemicals involved: oxygen (O2), water (H2O), sulfur dioxide
(SO2), sulfur trioxide (SO3) and sulfuric acid (H2SO4).

Flow package is one of the most important elements for HYSYS simulation. As a
non-idealized system is used for this simulation, a PRSV equation of state is used as a fluid
package in the sulfuric acid concentration and the decomposition simulation.
 11

Thus reaction and reactor choice is the most important part in the sulfuric acid
decomposition part. Once the sulfur trioxide is produced from sulfuric acid decomposition,
it will immediately decompose to sulfur trioxide and oxygen. To simplify the process, the
decomposition is assumed to be separated into two steps. In the first step, sulfuric acid is
assumed to decompose into water and sulfur trioxide (H2SO4= SO3+ H2O). Next the sulfur
trioxide decomposes to oxygen and sulfur dioxide (2SO3= 2SO2+ O2). Thus two reaction
and two reactors should be choose for both of the two steps.

Firstly because of first reaction (H2SO4= SO3+ H2O) is not a kinetic reaction, the
conversion reaction is carried for this step. The conversion is assumed 90% in this
simulation. A plug flow reactor model is should be most suitable for this reaction. But the
conversion reaction is not suitable for this reactor. Therefore a conversion reactor is carried
in this step.

The second reaction (2SO3= 2SO2+ O2) is a kinetic reaction. The reaction is taken in this
step, where the reaction rate is based on: r = k * f(basis) k * f(basis), where k = A exp{-
E / RT} * T^. The activation energy (E) is assumed to be 17.46 kcal/mol/K, and
pre-exponential factor (A) is assumed as 2.45*108h-1. And no heat loss is assumed for all
the reactors and heat exchangers for the simulation.

3.3 Description of the simulation

It is a big process simulation. First there are two separate simulations for each step of
H2SO4 concentration and H2SO4 decomposition to make those two steps easily and clearly
seen. The connection fluids (11 and 13) between the two steps were assumed for the two
separate simulations based on each others result. Then a whole process simulation of
section II was made for the energy analyzing.

3.3.1 H2SO4 concentration simulation

Graph 2 shows the HYSYS simulation for H2SO4 concentration part in section II. In this
 12

part it can divide into two parts. Fluid 1-11 is actually the concentration part. Fluid 13-45 is
carried for the gas separation and heat recovery.

GRAPH 2. HYSYS simulation for H2SO4 concentration part in section II

Fluid 1 from section I, contains mostly water (H2O) and sulfuric acid (H2SO4), and a small
amount of sulfur dioxide (SO2), and then decreases the pressure from 180 kPa to 8 kPa and
goes through three separators (S1,S2 and S3) to get the H2SO4 concentrated. This means
fluids 3, 6and 10 are mostly water vaporized from the separators. After the separation,
steam 11 is concentrated to be composition.

Fluid 13 from the H2SO4 composition contains gas sulfur dioxide (SO2), oxygen (O2) and
some water (H2O). In other part of this simulation two additional separators (S4 and S5)
are carried to separate the gas sulfur dioxide (SO2) and oxygen (O2) with water (H2O).
Five heat exchangers (HX1-1, HX1-2, HX2, HX4 and HX5) are carried to recycle the heat
energy.
 13

Finally fluids 35 and 45 come out from the whole process. It is mainly sulfur dioxide (SO2)
and oxygen (O2) that come out in fluid 35, and go back to section I. Fluid 45 contains
mostly water (H2O), and it goes back to section I.

3.3.2 H2SO4 decomposition simulation

Graph 3 shows about HYSYS simulation for H2SO4 decomposition step. All the reactions
are in this part.

GRAPH 5. HYSYS simulation for H2SO4 composition part of section II

Fluid 11 which comes from the concentration part is pumped into the absorption column to
accomplish sulfur acid purification. In the absorption column (Absorber), sulfur trioxide is
assumed to be totally reacting back to sulfuric acid as H2O + SO3 = H2SO4. Thus fluid 13
which comes out from the absorption column to the concentration part contains only sulfur
dioxide (SO2), oxygen (O2) and water (H2O).

High temperature heat is needed for the sulfuric acid decomposition reaction. Nuclear
 14

energy is considered the best choice for the high temperature reaction. There are various
nuclear reactor types built for this reaction: pressurized water-cooled reactors, organic
cooled reactors, alkali metal-cooled reactors, heavy metal-cooled reactors, boiling
water-cooled reactors, molten salt-cooled reactors, liquid-core reactors, gas-core reactors
and gas cooled reactors. Sandia National Laboratories evaluated the nuclear reactors by
their safety, economic and operational issues. The helium gas-cooled reactor was
recommended as the most suitable for this reaction. It has been widely used around the
world. (Schultz 2003.)

But the helium gas-cooled reactor cannot be found in HYSYS. A common reactor model is
taken for H2SO4 decomposition (H2SO4= SO3+ H2O) and a plug flow reactor model is
taken for SO3 decomposition (2SO3= 2SO2+ O2) instead of the helium gas-cooled reactor.
Thus the efficiency of the simulation cannot be as high as using the helium gas-cooled
reactor. Actually, the temperature needed in the first step reaction is not very high, the
temperature in the common reactor is around 380 C with the high presser 1200 kPa. A
high temperature is required for the second reaction in the plug flow reactor at 650-850C
and with a high pressure 1200 kPa.

Between the two reactors, there is a heater, which heats up the steam to a higher
temperature for further reaction. Actually the two reactions cannot be separated to two
reactions. Sulfuric acid (H2SO4) is assumed to be decomposed into sulfur trioxide (SO3)
and water (H2O) at the lower temperature around 380C, and react in another reactor at
higher temperature to decompose trioxide (SO3).

3.3.3 The whole process simulation

Based on the two separate simulations, the whole process simulation (Graph 4) is easily to
build.
 15

GRAPH 4. HYSYS simulation for the whole process of sulfuric acid decomposition
 16

As two separate part simulations are based on assumptive data of fluids 11 and 13. They
cannot be used for the further analysis. The whole simulation made for it. The mole flow
out of the process and the energy balance is going to be analyzed by HYSYS at the
different temperatures from 650 to 850C. An overview of this simulation clearly shows
that the fluid 1 flow into the process, fluid 35 and 45 come out with the production from
this process. And the red arrowhead in the graph shows all the heat flow in this simulation.
 17

4 RESULTS AND DISCUSSION

4.1 The workbook of the HYSYS simulation

The workbook of the HYSYS simulation is directly calculated by HYSYS. Table 1 shows
the vapor fraction, temperature, pressure, the mole flow and the mole fraction of the five
compounds of all the streams flowing in the process at 850C.

TABLE 1. Mass balance and five compounds mole fraction at 850C

Molar Mole Fraction

Vapour T P
Flow
Fraction (C) (kPa) O2 H2O SO2 SO3 H2SO4
kmol/h
1 0.0019 119.90 180 5.4053 - 0.8036 0.0007 - 0.1957
2 0.7526 74.05 8 5.4053 - 0.8036 0.0007 - 0.1957
3 1.0000 74.05 8 4.0680 - 0.9990 0.0010 - 0.0000
4 - 74.05 8 1.3373 - 0.2092 0.0000 - 0.7908
5 0.1266 94.35 8 1.3373 - 0.2092 0.0000 - 0.7908
5-1 0.1262 94.23 8 1.3373 - 0.2092 0.0000 - 0.7908
6 1.0000 94.35 8 0.1693 - 1.0000 0.0000 - 0.0000
7 - 94.35 8 1.1681 - 0.0946 0.0000 - 0.9054
8 - 94.35 20 1.1681 - 0.0946 0.0000 - 0.9054
9 0.0567 151.90 20 1.1681 - 0.0946 0.0000 - 0.9054
10 1.0000 151.90 20 0.0662 - 1.0000 0.0000 - 0.0000
11 - 151.90 20 1.1019 - 0.0402 0.0000 - 0.9598
12 - 151.85 1,200 1.1019 - 0.0402 0.0000 - 0.9598
13 1.0000 201.28 1,200 2.6882 0.1967 0.4099 0.3934 0.0000 0.0000
14 - 172.55 30 1.0776 0.0000 0.0157 0.0002 0.0000 0.9841
15 - 172.50 1,200 1.0776 0.0000 0.0157 0.0002 0.0000 0.9841
16 - 384.20 1,200 1.0776 0.0000 0.0157 0.0002 0.0000 0.9841
16-0 - 379.40 1,200 1.2010 0.0000 0.0202 0.0001 0.0013 0.9784
16-2 - 335.30 1,200 0.1234 0.0000 0.0590 0.0000 0.0123 0.9288
16-3 - 335.30 1,200 0.1234 0.0000 0.0590 0.0000 0.0123 0.9287
16-1 1.0000 335.30 1,200 2.1352 0.0000 0.5032 0.0001 0.4953 0.0014
17 1.0000 850.00 1,200 2.1352 0.0000 0.5032 0.0001 0.4953 0.0014
18 1.0000 850.00 1,200 2.6640 0.1985 0.4034 0.3971 0.0000 0.0011
19 0.9988 271.12 1,200 2.6640 0.1985 0.4034 0.3971 0.0000 0.0011
19-1 0.9988 271.13 1,200 2.6639 0.1985 0.4033 0.3971 0.0000 0.0011
20 1.0000 60.86 20 0.0662 - 1.0000 0.0000 - 0.0000
21 1.0000 60.86 20 0.0199 - 1.0000 0.0000 - 0.0000
22 1.0000 60.86 20 0.0463 - 1.0000 0.0000 - 0.0000
23 1.0000 243.42 83 0.0463 - 1.0000 0.0000 - 0.0000
 18

TABLE 1. Mass balance and five compounds mole fraction at 850C (cont.)

Molar Mole Fraction

Vapour T P
Flow
Fraction (C) (kPa) O2 H2O SO2 SO3 H2SO4
kmol/h
24 1.0000 135.00 83 0.0463 - 1.0000 0.0000 - 0.0000
25 1.0000 95.00 83 0.0463 - 1.0000 0.0000 - 0.0000
25-1 - 94.34 83 0.0463 - 1.0000 0.0000 - 0.0000
26 - 94.41 570 0.0463 - 1.0000 0.0000 - 0.0000
27 0.8518 139.95 1,200 2.6882 0.1967 0.4099 0.3934 0.0000 0.0000
28 - 139.95 1,200 0.3984 0.0001 0.9739 0.0260 0.0000 0.0000
29 1.0000 139.95 1,200 2.2898 0.2309 0.3117 0.4573 0.0000 0.0000
30 0.8553 124.90 1,200 2.2898 0.2309 0.3117 0.4573 0.0000 0.0000
31 - 124.90 1,200 0.3313 0.0001 0.9666 0.0333 0.0000 0.0000
32 1.0000 124.90 1,200 1.9585 0.2700 0.2010 0.5291 0.0000 0.0000
33 1.0000 127.14 1,200 1.9585 0.2700 0.2010 0.5291 0.0000 0.0000
34 0.9498 70.11 200 1.9585 0.2700 0.2010 0.5291 0.0000 0.0000
35 0.9520 70.40 200 1.9585 0.2700 0.2010 0.5291 0.0000 0.0000
36 1.0000 74.86 8. 4.2372 - 0.9991 0.0009 - 0.0000
37 - 52.17 20 4.2372 - 0.9991 0.0009 - 0.0000
38 - 52.24 570 4.2372 - 0.9991 0.0009 - 0.0000
39 - 59.00 20 0.0199 - 1.0000 0.0000 - 0.0000
40 - 59.07 570 0.0199 - 1.0000 0.0000 - 0.0000
41 0.0008 93.05 570 0.3313 0.0001 0.9666 0.0333 0.0000 0.0000
42 - 55.29 570 4.5885 0.0000 0.9967 0.0033 0.0000 0.0000
43 - 140.02 1,200 0.3984 0.0001 0.9739 0.0260 0.0000 0.0000
44 0.0453 140.00 570 0.3984 0.0001 0.9739 0.0260 0.0000 0.0000
45 - 63.93 570 5.0331 0.0000 0.9949 0.0050 0.0000 0.0000

There are four more different workbooks for the simulation by changing the temperature
850C in streams 17 and 18 to 650C, 700C, 750C and 800C. Those five workbooks are
the basic data for further statistic.

4.2 Mass balance of the process

Table 2 shows the mole flow in stream 1 from section I, and it is assumed the same mole
flows into the process for all decomposition at five different temperatures. Sulfuric acid
(H2SO4) flows into this process to get hydrogen (O2), water (H2O) and sulfur dioxide
(SO2).
 19

TABLE 2. The mole flow in from stream 1

O2 H2O SO2 SO3 H2SO4

(kmol/h) (kmol/h) (kmol/h) (kmol/h) (kmol/h)
Stream 1 - 4.3437 0.0038 - 1.0578

Streams 35 and 45 are the flow out from this process. They contain hydrogen (O2), water
(H2O) and sulfur dioxide (SO2). The data in Table 3 and Table 4 show that the productions
from different temperatures are similar. Thus the average mole flow out of the process
calculated from those data for streams 35 and 45.

TABLE 3. The mole flow out from stream 35 at different temperatures

O2 H2O SO2 SO3 H2SO4

stream 35
(kmol/h) (kmol/h) (kmol/h) (kmol/h) (kmol/h)
650 C 0.5287 0.3696 1.0364 - -
700 C 0.5287 0.3696 1.0364 - -
750 C 0.5287 0.3696 1.0362 - -
800 C 0.5287 0.3696 1.0362 - -
850 C 0.5287 0.3696 1.0362
Average 0.5287 0.3696 1.0362 - -

TABLE 4. The mole flow out from stream 45 at different temperatures

O2 H2O SO2 SO3 H2SO4

stream 45
(kmol/h) (kmol/h) (kmol/h) (kmol/h) (kmol/h)
650 C - 4.9969 0.0251 - -
700 C - 5.0071 0.0254 - -
750 C - 5.0091 0.0254 - -
800 C - 5.0086 0.0254 - -
850 C - 5.0077 0.0254 - -
Average - 5.0059 0.0253 - -

However there is 4.3237kmol/h water (H2O) and 0.0038kmol/h sulfuric acid (H2SO4)
contained in the inlet flow. For the mass balance it should be subtract from the productions.
Hence Table 5 is made for the total mass flow.
 20

TABLE 5. Total mass flow

O2 H2O SO2 SO3 H2SO4

(kmol/h) (kmol/h) (kmol/h) (kmol/h) (kmol/h)
Flow in 1 - 4.3437 0.0038 - 1.0578
Flow out 35 0.5287 0.3696 1.0362 - -
Flow out 45 - 5.0059 0.0253 - -
Total out 0.5287 5.3755 1.0615
Reactant - - - - 1.0578
Products 0.5287 1.0318 1.0577 - -

The mass balance calculation:

2 H2SO4 = 2 H2O + 2 SO2 + O2
2 mol 2 mol 2 mol 1mol
From calculation 1.0578mol 1.0578mol 1.0578mol 0.5289mol
From HYSYS 1.0578mol 1.0318mol 1.0577mol 0.5287mol

Compare the data from calculation with HYSYS simulation analysis. The error is not very
significant. There is just a little bit difference for the water (H2O). The error comes from
the simulation at 650C.

4.3 Energy requirement and efficiency

TABLE 6. The energy flow between 650C to 850C

650 C 700 C 750 C 800 C 850 C

CE1 - 184,149.80 - 184149.80 - 184,149.80 - 184,149.80 - 184,149.80
CE2 845.80 845.80 845.80 845.80 845.80
CE3 1,899.63 1899.63 1,899.63 1,899.63 1,899.63
CE4 - 2.33 - 2.35 - 2.36 - 2.32 - 2.36
COE 291.41 291.41 291.41 291.41 291.41
EV1 140,101.63 140101.63 140,101.63 140,101.63 140,101.63
EV2 527.26 509.42 507.11 507.74 508.86
EV3 - 769.21 - 795.57 - 799.78 - 798.76 -796.70
EXPE 7,516.66 7515.47 7,515.45 7,515.59 7,515.47
HE 67,796.97 65699.87 64,068.40 62,710.90 64,181.47
PE1 0.93 0.93 0.93 0.93 0.93
PE2 93.01 93.01 93.01 93.01 93.01
PE3 144.35 120.07 103.91 93.97 92.88
 21

TABLE 6. The energy flow between 650C to 850C (cont.)

PE4 0.57 0.57 0.57 0.57 0.57

PE5 56.83 56.83 56.83 56.83 56.83
PE6 0.27 0.27 0.27 0.27 0.27
R1 234,160.18 237012.51 239,087.14 240,648.04 239,522.90
R2 102,458.41 102114.91 101,776.86 101,441.21 101,116.19
SUM 370,972.57 371,314.61 371,397.01 371,256.65 371,278.99

Table 6 depicts the energy requirement for various unit operations at temperature raising
from 650 to 850C and the sum of the energy supplied in this process.

The overall thermal efficiency of the process is calculated by the formula:

= Qreaction / Qi
Where : Thermal efficiency of the process
Qreaction : Overall reaction enthalpy of the sulfuric acid decomposition
Qi : Total thermal energy supplied to the process

The reaction enthalpy of the sulfuric acid decomposition Qreaction is 278.643kJ/mol. The
total thermal energy supplied is presented in Table 6. (ztrk, et al. 1995,16.)

650C = Qreaction / Qi = 278.643 / 370.973 = 75.11%

700C = Qreaction / Qi = 278.643 / 371.315 = 75.04%
750C = Qreaction / Qi = 278.643 / 371.397 = 75.03%
800C = Qreaction / Qi = 278.643 / 371.257 = 75.05%
850C = Qreaction / Qi = 278.643 / 371,279 = 75.05%

From the calculation, the efficiency of the process got the highest value at the temperature
650C. But the efficiency at each temperature does not change a lot. The efficiency
difference from 700 to 850C is only 0.02%.
 22

5 CONCLUSION

The Sulfur-Iodine thermochemical water-splitting cycle is an effective and reasonable way

for hydrogen (H2) producing. And there are not any harmful byproducts or emissions from
the process. Just water (H2O) in and oxygen (O2) and hydrogen (H2) out. Heat is the only
thing it needed in this process. It can be heated by nuclear source, and it can be also
powered by solar energy. It is considered as the idea environmental solution for hydrogen
produce.

The first aim of this thesis was constructing a simulation for sulfuric acid decomposition
by HYSYS. In this thesis there were three simulations constructed: Two separate
simulations for H2SO4 concentration and H2SO4 decomposition, and one whole process
simulation. It shows a good result. The mass balance is almost the same with that
calculated by the reaction equation.

For the thermal efficiency of the process a very good result is reported 75.03-75.11%.
Comparing the result with Bilgens flowsheet with a high thermal efficiency of about 77%,
the thermal efficiency reported in this thesis seems not so good. But for the temperature
stability of the Bilgens process is not so high. It can not react under 720C. But the
stability is much better by this HYSYS simulation, it still gets a high thermal efficiency at
the temperature 650C. But no heat loss is considered in this whole process. It can not get
so high thermal efficiency with for operation.
 23

REFERENCES

Brown, L. 2006. Large Scale H2-Prodction by HTR The Sulfur Iodine Process.
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Brown, L. 2007a. Evolution of the Sulfur-Iodine Flow Sheet. American Institute of

chemical engineers. Salt Lake City, Utah.

Brown, L. 2007b. Thermiochemical Water-splitting and the US Nuclear Hydrogen

Programme. Sustainable Hydrogen Production, a role for fusion. Oxford, UK.

Crosbier, L.M. and Chapin, D. 2003. Hydrogen Production by Nuclear Heat.

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Gilardi, T., Rodriguez, G., Gomez, A., Leybros, J., Borgard, J.M., Calrles, P. and Anzieu, P.
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Available: [Link]
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 24

Matthew, B. R. and Shenoy, S. A. 2005. Hydrogen Production Plant Using the Modular
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