The operating characteristics of hydrogen iodide (HI) decomposition for hydrogen production were investigated using the commercial computational fluid dynamics code, and various factors, such as hydrogen production, heat of reaction, and temperature distribution, were studied to compare device performance with that expected for device development. Hydrogen production increased with an increase of the surface-to-volume (STV) ratio.
Trang 1Original Article
TWO-DIMENSIONAL SIMULATION OF HYDROGEN IODIDE
DECOMPOSITION REACTION USING FLUENT CODE FOR
HYDROGEN PRODUCTION USING NUCLEAR TECHNOLOGY JUNG-SIK CHOIa, YOUNG-JOON SHINb, KI-YOUNG LEEb, and JAE-HYUK CHOI c,*
aThe Institute of Machinery and Electronic Technology, Mokpo National Maritime University, 91 Haeyangdaehak-ro, Mokpo-si, Jeollanam-do, South Korea
bKorea Atomic Energy Research Institute, Daedeok-Daero 989-111, Yuseong-gu, Daejeon, South Korea
cDivision of Marine Engineering System, Korea Maritime and Ocean University, 727 Taejong-ro, Yeongdo-gu, Busan, South Korea
a r t i c l e i n f o
Article history:
Received 5 October 2014
Received in revised form
5 January 2015
Accepted 24 January 2015
Available online 27 March 2015
Keywords:
Computational fluid dynamics
Fluent code
Hydrogen iodide decomposition
reaction
Hydrogen production
Sulfureiodine cycle
a b s t r a c t
The operating characteristics of hydrogen iodide (HI) decomposition for hydrogen pro-duction were investigated using the commercial computational fluid dynamics code, and various factors, such as hydrogen production, heat of reaction, and temperature distribu-tion, were studied to compare device performance with that expected for device devel-opment Hydrogen production increased with an increase of the surface-to-volume (STV) ratio With an increase of hydrogen production, the reaction heat increased The internal pressure and velocity of the HI decomposer were estimated through pressure drop and reducing velocity from the preheating zone The mass of H2O was independent of the STV ratio, whereas that of HI decreased with increasing STV ratio
Copyright© 2015, Published by Elsevier Korea LLC on behalf of Korean Nuclear Society
1 Introduction
Hydrogen not only has potential for use as an alternative to
fossil fuels, but also plays a key role in solving what is known
as a trilemma (economic growth, energy use, and
environ-mental degradation)[1] A number of thermochemical cycles
were first postulated by Funk and Reinstrom[2]as the most efficient way to produce fuels (e.g., hydrogen, ammonia) from stable and abundant species (e.g., water, nitrogen) using heat sources
2H2Oþ SO2þ I2/ H2SO4þ 2HI
* Corresponding author
E-mail address:choi_jh@kmou.ac.kr(J.-H Choi)
This is an Open Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http:// creativecommons.org/licenses/by-nc/3.0) which permits unrestricted non-commercial use, distribution, and reproduction in any me-dium, provided the original work is properly cited
Available online at www.sciencedirect.com
ScienceDirect
j o u r n a l h o m e p a g e :h t t p : / / w w w j o u r n a l s e l s e v i e r c o m / n u c l e a r
-e n g i n -e -e r i n g - a n d - t -e c h n o l o g y /
http://dx.doi.org/10.1016/j.net.2015.01.006
1738-5733/Copyright© 2015, Published by Elsevier Korea LLC on behalf of Korean Nuclear Society
Trang 22HI / H2þ I2
H2SO4/ H2Oþ SO2þ 1/2 O2
In a closed cycle system, various related processes have
been proposed and have received a great deal of attention The
sulfureiodine (SI) process involving thermochemical
hydrogen production using nuclear energy was proposed by
General Atomics and this technology has been studied by
many researchers[3e5]
Extensive research on hydrogen iodide (HI) decomposition
for hydrogen production has been carried out for experimental
verification and measurement of several factors, such as
con-version efficiency and kinetics[6] The decomposition of HI is
the key to producing hydrogen in the SI cycle The
decompo-sition of HI in the absence of any catalysts is not efficient even
at 773.15 K; therefore, catalysts have been used to promote this
reaction[7] Moreover, the rate of the homogeneous gas-phase
reaction is considerably low at temperatures<700 K Thus, it is
desirable to use a catalyst to increase the reaction rate, which
has led to the study of platinum catalysts[8e10] A
decompo-sition test using 98% pure HI gas was carried out by Ilda[8]in
1978 using a platinum supported on polytetrafluoroethylene
catalyst Moreover, Wang et al.[11]investigated the effects of
different supports (carbon nanotubes, active carbon, carbon
molecular sieve, graphite, and Al2O3), masses of catalyst, and
reaction temperatures on the decomposition of HI Fresh and
used active carbon-supported platinum catalysts were also
characterized Furthermore, different types of catalysts
including noble metals and support materials (active carbon
[7,12], Pt[13], Ni[14], and bimetallic catalysts[6]) have been
reported to catalyze HI decomposition
To date, much progress has been made on the efficiency of
this process However, insufficient research has been
con-ducted on the role of water vapor in the HI decomposition
process In addition, very few reports have been published on
the kinetic studies of HI decomposition in the presence of H2O
Assessment of the real potential of the HI decomposition
re-action requires a deep knowledge of the thermodynamic
behavior of hydrogen production systems Improving the
ef-ficiency of hydrogen production and optimizing the reactor
requires an understanding of the thermodynamics of the
process The thermodynamic model for the HIxsystem used
by Roth and Knoche was proposed by Neumann[15]in 1987,
and was based mostly on total pressure measurements
per-formed at Rheinisch-Westf€alische Technische Hochschule
(RWTH) Aachen[16]and on liquideliquid equilibrium data In
the simulation studies, hydrogen pressures higher than those
expected for homogeneous gas-phase HI decomposition in the
direct decomposition of HIeH2OeI2solution were achieved
[17] Berndh€auser et al.[18]compared the calculated
homo-geneous gas-phase reaction results with those of direct HI
decomposition from HIeH2OeI2solutions, and found that the
rate of direct HI decomposition was several orders of
magni-tude higher than that of the gas-phase reaction Furthermore,
Lanchi et al.[19], Murphy and O'Connell[20], and Hadj-Kali
et al.[21], reviewed the phase equilibrium properties of the
HIeI2eH2O (HIx) system and proposed new thermodynamic
models for describing the thermodynamic properties of this
system Many researchers have attempted to develop
appro-priate models for the HI decomposition reaction in the SI
process[22,23] Commercial process simulators such as Aspen Plus (Aspen Technology, Inc., Massachusetts, USA) [24e26] and ESP (simulator program, Microsoft, USA) [27e29] have been used to develop these thermodynamic models
In addition, in recent years, interest in and research on nu-clear hydrogen technology, which involves direct decomposi-tion of water to produce a large amount of hydrogen at high temperatures in a nuclear reactor as the heat source of the thermochemical cycle, has increased [30,31] In particular, following the successful continuous operation of a bench-scale closed cycle gas turbine by the Japanese Atomic Energy Agency,
SI thermochemical hydrogen production technology has taken center stage as one of the high-practical-potential hydrogen production technologies that could be coupled with the very high temperature reactor (VHTR) [32e36] However, trans-ferring the high heat output of the gas coolant for VHTR to the SI thermochemical cycle involves the great challenge of devel-oping a heat-exchanger material capable of withstanding high temperatures (1173 K) and pressures (approximately 50e70 kg/
cm2) In the HI decomposition reaction, which requires a lot of heat in the SI cycle, if the decomposition efficiency of HI can be maintained at high pressures, the design and development of the heat exchanger and reactor can be flexible
In this study, an optimum decomposition reactor in the thermochemical VHTReSI cycle operating characteristics of the HI decomposition reaction were investigated using the code Several factors, such as hydrogen production, heat of the reaction, and temperature distribution, were studied to compare the device performance with that expected for de-vice development
2 Materials and methods 2.1 Basic equation for the HI decomposition reaction The decomposition reaction of HI is as follows:
In this study, the simulation was performed using the LangmuireHinshelwood-type rate equation on the catalytic decomposition of HI in the presence of an active carbon catalyst proposed by Oosawa et al.[13]
RHI¼ xHI
1þ KI 2PxI 2
ffiffiffiffiffiffiffiffiffiffiffiffiffi
xH 2xI 2
p 1þK PF e
2
Kp
1þ KI 2PxI 2
where
KHI¼ 0:158 exp
8; 250 cal$mol1
RT
(4)
KI 2 ¼ 5:086 1011exp
16; 480:1 cal$mol1
RT
(5) whereFeis the equilibrium conversion, rHI(mol/m3/s) is the reaction rate, k (mol/m3/Pa/s) is the reaction rate coefficient,
Trang 3P (Pa) is the system pressure, xHI, xI2, and xH2are the mole
fractions of HI, I2, and H2, respectively, KI2is the absorption
equilibrium constant of iodine (1/Pa), and Kpis the equilibrium
constant for the decomposition of HI Further, Kpcan be
ob-tained from HSC 5.1 (chemistry-software, USA)[37]as follows:
Kp¼
Ce
H 2
0:5
Ce
I 2
0:5
Ce
HI
(6)
Fe¼ 1 CeHI
CHI;in¼ 1
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
CeH2
CeI2 q
Kp¼ 4:515 103 4:519 105Tþ 1:437 107T2
8:662 1011T3þ 1:828 1014T4 (8)
where Ce
H2(mol/m3), Ce
I2(mol/m3), and Ce
HI(mol/m3) are the equilibrium concentrations of H2, I2, and HI, respectively, CHI,in
(mol/m3) is the inlet concentration of HI, and T (K) is the
re-action temperature
2.2 Model design
The reactive distillation flow sheet developed by GA Company
(General Atomics, San Diego, CA, USA)[38]is shown inFig 1
Fig 1A illustrates the HI decomposition section The dashed
line inFig 1B shows the multistage distillation column for the periodic acid solution and the HI decomposer
The HIeI2eH2O mixture gas was discharged from the condenser part of the multistage distillation column for the HI reaction, and flowed into the HI decomposer Then, the H2eI2
gas was generated after decomposition of the mixture gas In this study, the characteristics of the thermal decomposition device (HI decomposer,Fig 2A) were investigated using the CFD simulator model (Fig 2B)
Fig 2A shows the HI decomposer model and the heating device consisting of a sealed three-stage electric heater A Hastelloy HC276 tube was inserted, and its outer diameter, inner diameter, and height were 60.5 mm, 52.7 mm, and
1500 mm, respectively This tube was filled with active carbon catalyst and Al2O3 Raschig ring Each of the three electric heaters had built-in heating elements (i.e., 3.65-kW Kanthal A-1) and the HC276 tube was surrounded by a low-density ceramic fiber board for insulation Moreover, a proportional-integral-derivative controller was used to maintain the tem-perature of the three electric heaters at a set value The
HIeI2eH2O mixture gas discharged from the condenser of the multistage distillation flowed into the bottom of the inlet of the HI decomposer at an absolute pressure of 5 kgf/cm2
(506,625 Pa) The temperature gradually increased to reach the set temperature of the electric heater of the HI decomposer and was maintained at this value Meanwhile, helium (He) gas
or N2gas was supplied to the HI decomposer to maintain the
Fig 1e Reactive distillation flow sheet in the SI cycle (A) HI decomposition section (B) Multistage distillation column and HI decomposer DI, deionized; HI, hydrogen iodide; SI, sulfureiodine
Trang 4pressure at 506,625 Pa, and thermal equilibrium was achieved
using an external heating chamber of the HI decomposer The
mixture gas was supplied to the inlet under the conditions
that the temperature reached the set point and the pressure
was reliably maintained at 5 kgf/cm2
2.3 CFD analysis methods and boundary conditions of
the CFD domain
The CFD simulation model of the HI decomposer is presented
inFig 2B Size, properties, and boundary conditions identical
to those of the actual operating system were applied, and then
the CFD analysis was conducted using the Fluent program
Moreover, to describe the actual operating system, a
user-defined function was applied At t ¼ 0 and 464.85 K
(191.7 C), the HIeI2eH2O mixture gas with flow rates of
0.008 mol/s HI, 0.0002 mol/s I2, and 0.020 mol/s H2O was
injected into the HI decomposer at an absolute pressure of
5 kgf/cm2 Maintaining a fixed porosity of 0.4, the
tempera-tures of the electric heaters were set at 773.15 K (500C),
873.15 K (600C), and 973.15 K (700C) The porosity value was
approximately predicted by considering several parameters,
such as the reactor size, volume, catalyst density, catalyst
size, and amount of catalyst The effect of the surface-to-volume (STV) ratio on hydrogen production was also consid-ered When the reactor was developed, the STV ratio, defined
as the specific surface of the catalyst, was approximately 0.4 in the preliminary simulation The effects of setting the STV ratio at 0.3, 0.4, and 0.5 on hydrogen production and reaction heat were investigated
STV ratio¼ A/V where A is the surface area of the pore walls and V is the unit volume
For efficient CFD analysis, the following criteria were assumed:
The temperature of the heater was always maintained at the set temperature
N2gas was fully filled inside the HI decomposer, as the initial condition of the simulation
The backward (reverse) reaction was not considered
The absolute pressure and temperature were set at 5 kgf/
cm2 (506,625 Pa) and 673.15 K (400C), respectively, and then the mixture gas was injected
Fig 2e Designed HI decomposer for the SI cycle and the CFD model (A) Designed HI decomposer (B) CFD domain CFD, computational fluid dynamics; HI, hydrogen iodide; ID, internal diameter; OD, outer diameter; SI, sulfureiodine
Trang 53 Results and discussion
3.1 Effect of the heater temperature on hydrogen
production
To investigate the effects of the heater temperature on
hydrogen production, hydrogen production at HI decomposer
temperatures of 773.15 K, 873.15 K, and 973.15 K were
esti-mated at STV ratios of 0.3, 0.4, and 0.5, as shown inFig 3
Under each condition, the amount of hydrogen produced was
monitored at 10-minute intervals and the total operation time
was 180 minutes
773.15 K (heater temperature) Up to 20 minutes after the
operation of the HI decomposer (i.e., after the start of the
decomposition process), no hydrogen production occurred
regardless of the STV ratio From 20 minutes to 120 minutes,
the amount of hydrogen production varied according to the
STV ratio: the hydrogen production was 1.11e1.12 mol/h,
1.98e1.99 mol/h, and 3.09e3.10 mol/h at the STV ratios of 0.3,
0.4, and 0.5, respectively As presented inFig 3B, at 873.15 K,
the amount of hydrogen produced was very low for 20
mi-nutes, but after 120 mimi-nutes, it increased according to the STV
ratio After 120 minutes, hydrogen production was
1.11e1.12 mol/h, 1.98e1.99 mol/h, and 3.09e3.10 mol/h at STV
ratios of 0.3, 0.4, and 0.5, respectively.Fig 3C shows hydrogen
production at 973.15 K Similar to the reaction at 773.15 K and
873.15 K, the chemical reaction occurred, and then, hydrogen
was produced at 1.11e1.12 mol/h, 1.98e1.99 mol/h, and 3.09e3.10 mol/h at STV ratios of 0.3, 0.4, and 0.5, respectively
As shown in Fig 3AeC, hydrogen production was more strongly affected by the STV ratio than by the heat supplied by the heater The inner temperature of the HI decomposer was higher than the temperature for catalyst activation (T> 623.15 K) initially, and the inlet mass flow rate was the same regardless of the heater temperature
3.2 Reaction heat prediction with different STV ratios
Fig 4AeC presents the heat of the reaction at STV ratios 0.3, 0.4, and 0.5 The reaction was endothermic As shown in Fig 4A, at an STV ratio of 0.3, the reaction heat was measured
at different heater temperatures A similar consumption of reaction heat was observed regardless of the heater temper-ature After 60 minutes, the reaction heat required to produce hydrogen was 0.0827e0.0831 kW/h, whereas after 120 mi-nutes, when the hydrogen production was constant, it was 0.1116e0.117 kW/h Therefore, the reaction heat increased with the increase of hydrogen production regardless of the temperature of the heater.Fig 4B, C shows similar results at STV ratios of 0.4 and 0.5, respectively At an STV ratio of 0.4, the reaction heat was 0e0.1604 kW/h regardless of the heater temperature; however, it increased with increasing hydrogen production At an STV ratio of 0.5, the reaction heat was 0e0.2147 kW/h and showed a similar correlation with hydrogen production as that observed at the 0.4 STV ratio
Fig 3e Estimates of hydrogen production according to changes in heater temperature (A) Heater set value ¼ 773.15 K (B) Heater set value¼ 873.15 K (C) Heater set value ¼ 973.15 K STV, surface-to-volume ratio
Fig 4e Reaction heat according to different STV ratios (A) STV ratio 0.3 (B) STV ratio 0.4 (C) STV ratio 0.5 STV, surface-to-volume ratio
Trang 6Fig 5e Inner temperature of HI decomposer according to temperature changes of heater (A) Heater set value ¼ 773.15 K with different STV ratios at 160 minutes (B) STV ratio of 0.3 with different temperatures at 160 minutes (C) Heater set value¼ 773.15 K with different STV ratios at 160 minutes (D) STV ratio of 0.3 with different temperatures at 160 minutes
HI, hydrogen iodide; ITC, inner thermocouple; STV, surface-to-volume ratio
Trang 7As shown inFig 4AeC, the reaction heat used in the HI
decomposition reaction for hydrogen production was
corre-lated to the specific surface area of the catalyst and it had a
direct relation with the production of hydrogen However, the
temperature changes of the HI decomposer had no direct
ef-fect The mixture gas was introduced into the HI decomposer
when the heat supplied from the heater passed through the
decomposer completely and the temperature was higher than
the activation temperature (i.e., 673.15 K) Moreover, the
temperature of the mixture gas from the preheating zone was
increased up to the temperature needed for the catalyst
decomposition reaction Therefore, to enhance thermal
effi-ciency, lowering the temperature of the heater was more
ad-vantageous at the STV ratio
3.3 Dependence of the HI decomposer inner temperature
distribution on the heater temperature
The inner temperature distribution of the HI decomposer was
monitored at different temperatures (773.15 K, 873.15 K, and
973.15 K) at various STV ratios (0.3, 0.4, and 0.5) during an
operation time of 160 minutes (Fig 5AeC) Moreover, the
temperatures are presented in the form of area-weighted
av-erages at inner thermocouple (ITC) 1e5 The temperature at
the center of the catalyst zone was lower than that at the
preheating zone for all STV ratios (Fig 5A) The heat was used
to catalyze the decomposition reaction The temperatures of
the outlet part, which discharged the mixture gas, and the
temperature of the zone above the catalyst zone were
rela-tively higher than that of the catalyst zone The temperature
distribution was as follows: 778e801 K at ITC 1, 779e792 K at
ITC 2, 777e794 K at ITC 3, 790e805 K at ITC 4, and 789e820 K at ITC 5, regardless of the STV ratio
Especially, at an STV ratio of 0.3, the temperatures of ITC
1, ITC 2, and ITC 3 at 973.13 K were higher than the tem-peratures at 773.15 K and 873.15 K for the same STV ratio (Fig 5B) Because the decomposition is an endothermic re-action, it seems that less reaction heat was supplied, and therefore the inner temperature was higher at 973.15 K than
in the other cases Using different STV ratios, there was no significant difference in all of the temperatures However, different trends were exhibited at various temperatures even if the differences were small At 973.15 K, the inner temperature was found to be higher than in the other cases The main reaction takes place well with the reaction tem-perature or more operation conditions, so it is not necessary
to supply the over temperature
3.4 Inner velocity and pressure of HI decomposer according to temperature change of heater
In Fig 6AeC, the static pressure and velocity magnitude at STV ratios of 0.3e0.5 after 160 minutes of operation are pre-sented at three different heating temperatures The static pressure and velocity magnitude are area weighted and averaged As shown for positions AeE, the static pressure was 2.71 Pa at position A (0 mm), 26.95 Pa at position B (10 mm), 18.66 Pa at position C (510 mm), 2.41 Pa at position D (1490 mm), and 2.25 Pa at position E (1500 mm) The mixture gas flowed to the preheating zone filled with the Al2O3Raschig ring and it collided with the solid Al2O3Raschig ring, thus generating high pressure Therefore, a pressure drop was Fig 5e (continued)
Trang 8evident from the increase of the pressure value When the
mixture gas from the preheating zone flowed to the catalyst
zone, a pressure drop was generated but the magnitude was
smaller than in the previous case
As shown for AeE, the velocity magnitude also had no cor-relation with the heater temperature and STV ratio The ve-locity was 0.016 m/s at position A (0 mm), 0.04 m/s at position B (10 mm), 0.016 m/s at position C (510 mm), 0.016 m/s at position Fig 6e Pressure and velocity of HI decomposer according to temperature changes of the heater (A) STV ratio 0.3, (B) STV ratio 0.4 (C) STV ratio 0.5 Heater set at 773.15 K, 873.15 K, and 973.15 K HI, hydrogen iodide; STV, surface-to-volume ratio
Trang 9D (1490 mm), and 0.14 m/s at position E (1500 mm) At the outlet
at position E, the velocity of the mixture gas was highest
(0.14 m/s) In the empty space (i.e., AeB), the velocity of the
mixture gas was 0.016e0.04 m/s, but it slowed down to 0.016 m/
s when the gas flowed to the BeD region that was filled with the
solid The gas collided with the solid upon decreasing the flow
rate, and then the resulting mixture gas was well dispersed
As shown in Fig 6AeC, the static pressure and velocity
magnitude were independent of the heater temperature and
STV ratio, and this could be attributed to the fact that the fluid
porosity was 0.4 in all cases Therefore, the pressure drop of the
flowing mixture gas and velocity drop were affected not by the
thermal heat and surface area involved in the catalyst reaction,
but were rather affected by fluid porosity (solid factor)
In conclusion, the CFD analysis for HI decomposition
simulation was performed by applying the actual operation
conditions and HI decomposer design Several factors, such as
hydrogen production, reaction heat, inner temperature,
pressure, velocity, and mass distribution of the HI
decom-poser, were investigated
The hydrogen production depended on the STV ratio In
this study, the predicted hydrogen production was
1.12 mol/h, 1.99 mol/h, and 3.10 mol/h for STV ratios of 0.3,
0.4, and 0.5, respectively The hydrogen production at an
STV ratio of 0.5 was higher than that at 0.3 by 2 mol/h
For the three different STV ratios, the heat required for the HI
decomposition reaction was investigated With an increase
in the amount of hydrogen production, the reaction heat
increased, and its value was 0.1117 kW/h, 0.1604 kW/h, and
0.2147 kW/h at STV ratios of 0.3, 0.4, and 0.5, respectively
The inner temperature of the HI decomposer was studied
in the form of contour images at ITC 1e5 A temperature
higher than 750 K was required to generate the reaction
stably In addition, at ITC 2 and ITC 3 in the center of the
catalyst zone, the temperature was 773e801 K, which was
lower than that at the preheating region
The inner pressure and velocity of the HI decomposer were
investigated through pressure drop and reducing velocity
starting from the preheating zone At this point, the
pres-sure drop was approximately 24 Pa and the reducing
ve-locity was 0.024 m/s
For future research, the effect of fluid porosity and STV
ratio on hydrogen production/reaction heat/hydraulic
ther-mal analysis of the HI decomposer will be studied The
find-ings of this research can be used as a basis for the optimal
design of the HI decomposer
Conflicts of interest
All contributing authors declare no conflicts of interest
Acknowledgments
This work was supported by the National Research
Founda-tion of Korea (NRF) grant funded by the Korean government
(MSIP; Grant No 53154-14)
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