i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 8 5 8 4 e8 5 9 4

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Evaluation of reaction kinetics for the catalyst used

in PCRD and study of channel affect on the same

Vikram Shukla a,b,*, Deepak Tyagi c, Salil Varma a,c, B. Saha c,

A.N. Shirsat c, Sunil Ganju d, S. Sengupta b, S. Bhattacharya b,
N.K. Maheshwari a,e
a
Homi Bhabha National Institute, Mumbai, India
b
Research Reactor Design & Projects Division, Bhabha Atomic Research Centre, Mumbai, India
c
Chemistry Division, Bhabha Atomic Research Centre, Mumbai, India
d
Department of Atomic Energy, Mumbai, India
e
Advanced Heavy Water Reactor Division, Bhabha Atomic Research Centre, Mumbai, India

highlights

Kinetics of indigenous PCRD catalyst for Indian NPP has been experimentally studied.

Behavior of catalyst plates stacked in parallel inside PCRD has also been evaluated.

Variation in migration mechanism of reactants to catalyst surface affects behavior.

Overall affect has been empirically approximated as single step Arrhenius equation.

This is significant in modelling of PCRDs for faster containment analysis using CFD.

article info abstract

Article history: Hydrogen mitigation strategies have gained importance for Nuclear reactors owing to
Received 5 November 2019 damage caused to integrity of reactor containment by hydrogen fire in three major nuclear
Received in revised form accidents of Three Miles Island, Chernobyl and Fukushima. One promising technology for
8 January 2020 hydrogen mitigation is deploying Passive Catalytic Recombiner Devices (PCRDs). Principle
Accepted 13 January 2020 involved here is recombining hydrogen released during accident with oxygen from
Available online 12 February 2020 ambient air inside reactor containment on catalyst surface to form steam. Present work
focuses on experimental evaluation of reaction kinetics associated with hydrogen-oxygen
Keywords: recombination on surface of indigenous PCRD catalyst developed for Indian Nuclear Power
Nuclear power plants Plants. Behavior of catalyst plates stacked in parallel inside PCRD has also been evaluated.
Severe accidents This effect is due to difference in migration mechanisms of reactants and products to and
Hydrogen mitigation from the catalyst surface. Overall affect has been empirically approximated as single step
Noble metal catalyst Arrhenius equation. This is significant in modelling of PCRDs for faster containment
Hydrogen-oxygen recombination analysis using CFD.
Reaction kinetics © 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author. Homi Bhabha National Institute, Mumbai, India.

E-mail addresses: vikrams@barc.gov.in, vikramshukla.barc@gmail.com (V. Shukla).
https://doi.org/10.1016/j.ijhydene.2020.01.091
0360-3199/© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 8 5 8 4 e8 5 9 4
Introduction
Under certain postulated severe accident scenarios in Nuclear
Power Plants (NPPs), the behaviour of large amount of hydrogen
released from the metal-water reaction (over short duration)
and from radiolysis (over extended duration) needs to be
assessed and the consequences arising thereof need to be
mitigated [1]. The containment being a complex network of
interconnected rooms/halls, corridors, stair-ways, passages
etc., it is quite likely that the released hydrogen may get
distributed in a non-uniform way resulting in formation of
hydrogen-rich pockets in several or a few localised areas of the
building. It is well known that hydrogen-air mixtures with
hydrogen concentration higher than 4% (v/v) are combustible
and at further higher concentrations can even become deto-
nable. Any such combustion and/or detonation of hydrogen-air
mixture within the containment building can cause damage to
the concrete containment building and affect its integrity.
Many methodologies and technologies have been investi-
gated and tried in the past decade or so to mitigate the prob-
lem of hydrogen build-up inside the containment in the event
of a postulated accident [2,3]. Some of these methods and
important aspects related to them are listed below:
Deliberate Ignition: Early deliberate ignition of hydrogen is
adopted under this approach before it reaches dangerous
concentration levels in the gas mixture. The problem associ-
ated with this method is that hydrogen mixtures leaner than
4% (v/v) are very difficult to ignite, and in mixtures beyond 8%
(v/v) it is very difficult to control the combustion process,
which may lead to detonation. Moreover, the igniters fail to
perform under wet atmospheric conditions.
Homogenization (mixing): The containment atmosphere is
homogenized in order to prevent localized concentration
build-up in some compartments or regions of the contain-
ment. This method has two options.
Use of fans for mixing the containment atmosphere: It has the
disadvantage that it depends on electrical power, which in
most accident scenarios, may not be available. Also, it can
provide a source of ignition to the hydrogen mixture in the
form of an electrical spark.
Inerting: Pre-inerting involves replacing the containment
atmosphere with inert gases like pure nitrogen or carbon di-
oxide before every start-up. Post-inerting involves releasing
large amount of inert gases immediately after the onset of an
accident. This method basically deprives the containment
atmosphere of oxygen, thereby the flame, if any, gets starved
of the supporting oxygen.
Injecting helium in the lower portions of the containment,
so that it reduces the overall density of gas mixture in the
lower region and promotes natural convection towards upper
regions of the containment. The drawback of the method is its
sluggish effectiveness, dependence on the remote activation
of number of valves, and storage of large quantity of helium in
the plant.
While pre-inerting causes restrictions on entry of opera-
tors in the reactor building for any maintenance work, the
common disadvantage with both these method is that these
can be used only in smaller containments like that of BWRs
where the total gas volume is relatively low.
8585
Passive Catalytic Recombiner Device (PCRD): These devices
work on the principle of passively recombining (oxidising)
hydrogen with the oxygen from ambient air in the presence of
a catalytic surface to form steam and release heat [4]. The
presence of a catalyst enables the oxidation of hydrogen at
low (room) temperatures and thus eliminates the thermody-
namic consequences of a high temperature hydrogen-oxygen
reaction (like deflagration or detonation). This principle of
catalytic recombination of hydrogen is exploited in a
recombiner device by deploying several catalytic plates inside
a box, the lower portion of which is open for hydrogen to be
sucked in. Being exothermic in nature, the hydrogen-oxygen
reaction heats up the catalyst coated plates and this in turn,
heats up the hydrogen-air (or oxygen) mixture flowing over
the plates. The plates are placed side by side inside the box
and the hot gas mixture rises through the channels by buoy-
ancy. This sets up a natural convection loop because of
buoyancy. The establishment of the loop causes colder,
hydrogen rich mixture to be sucked in through the box inlet at
the bottom and a hotter, leaner mixture going out through the
box outlet at the top. Consequently, the overall hydrogen gas
concentration in the volume keeps on getting depleted in a
passive manner. A schematic of the recombiner device is
illustrated in Fig. 1.
The catalyst used for this purpose is primarily platinum
and palladium or a suitable combination of the two [5e7].
These devices have emerged as the most promising mitigation
technique due to their following inherent features:
(i) They are passive in the sense that they do not require
any external energy for their functioning or any
external stimulus for their start up.
(ii) They can function well over wide range of hydrogen
concentrations. This happens because the more the
hydrogen concentration, the more is the rate of reaction
and in turn, the more is the exothermic heat release
which causes enhanced natural circulation and hence
faster recombination. But this needs to be limited by the
maximum temperature attained at the catalytic surface
Fig. 1 e Schematic of PCRD.
8586 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 8 5 8 4 e8 5 9 4
which should always be less than the self-ignition
temperature of the gas mixture.
(iii) They are simple in construction and easy in application
as they consist of rectangular box having a set of par-
allel catalytic plates having flow channels between
them. Thus their handling, installation and mainte-
nance are relatively easy.
The development of catalyst for hydrogen oxidation dates
back to the work of Johann Wolfgang Dobereiner, who was the
first to study the catalytic features of platinum at the University
of Gena in Germany almost more than a century back. The first
application of the principle of catalytic recombination for miti-
gating hydrogen in NPPs was developed in Germany in 1986 as
reported by Chakraborty et al. [8]. It was a sandwich type
recombiner comprising of stainless steel carrier plates, over
which thin layers of platinum, vanadium and palladium were
vacuum deposited. These plates were stacked in an inert at-
mospheric condition maintained in a box to avoid contamina-
tion during plant operation and these were automatically
unfolded and lowered during an accident. After the develop-
ment of sandwich type recombiner, other type of catalytic
recombiners developed in Germany are (i) Box-Type Recombiner
- SIEMENS Design and (ii) Box Type Recombiner - NIS Design.
Subsequently, other countries also started their own R&D
for recombiner development. Reinecke published a paper on
Studies on innovative hydrogen recombiners as safety devices
in the containments of light water reactors [4]. Their study
was based on experiments carried at REKO facilities at For-
schungs Zentrum, Juelich (FZJ). The samples of sandwich type
plates were tested in laboratory scale test setup. In order to
demonstrate the functioning of the catalytic plates in large
volumes, two series of experiments, described as demon-
stration test and convection test, were performed in HDR test
facility. Development of catalytic recombiners in Canada has
resulted in two types of models based on natural convection
and on forced convection. The catalyst developed by AECL,
Canada consists of small platinum crystallites on a hydro-
phobic high surface area support, bonded to a stainless-steel
screen. The catalyst element for the forced convection test
was an open cylindrical module formed by wrapping up of
alternate layers of flat and corrugated screen with cylindrical
passages in between the catalyst layers. For the natural con-
vection test, the catalyst elements were in the form of loose
thin plates. The concept of using catalytic recombination of
hydrogen was also investigated at the Kurchatov Institute of
Technology, Russia, both experimentally and analytically.
Experiments were performed with flat plate type recombiners
comprising of catalytically activated high porosity cell mate-
rial (HPCM) in 1.2 m3 cylindrical shaped reaction vessel. Ex-
periments with both dry and wet air indicated effective
hydrogen combination with sufficiently small volumes of
HPCM. The HPCM samples made of stainless steel and
nichrome are the typical volumetrically regular structures of
periodically repeating cells, in the form of polyhedron with a
characteristic cell scale of approximately 1 mm. Material of
the walls of cells is generally small compared to overall vol-
ume of cells thereby causing highly porous (90%) structure
with low specific gravity. The walls of cell are covered with a
coating of aluminium oxide and platinum layer deposited by
magnetronic and electrochemical technique. The detailed
experimental data are not reported in open literature.
As part of the technology development programme for
hydrogen management in Indian Pressurised Heavy Water
Reactors (IPHWRs), experimental as well as analytical studies
are underway. The first type of catalyst device developed in
BARC, India was based on a chemically coated polyester cur-
tain. This curtain was proposed to be kept in a rolled position
and would roll down in the event of an accident. However, this
device could not perform beyond 150  C as the polyester cloth
showed its tendency to melt above this temperature. Hence,
its use was limited for very low hydrogen concentrations only.
Subsequently, metal substrate based catalyst devices have
been developed. Three different techniques for deposition of
the PtePd catalyst on polyester [9], cordierite honeycomb [10]
and stainless steel gauze [11] have been developed. Low sur-
face area catalysts viz. Pt, Pt þ Pd (simultaneous) and Pt þ Pd
(sequentially) deposited over stainless steel wire gauze,
employing single bath electroless reduction with formalde-
hyde as reducing agent has been developed and effect of
preparation route on overall morphology of noble metal
coating has been evaluated in detail [12]. This catalyst having
PtePd deposited simultaneously over stainless steel wire
gauze has been employed in PCRDs in Indian NPPs.
On the analytical front also many researchers have pub-
lished their studies in recent literature. ‘Modular Accident
Analysis Program version 5.04 (MAAP5.04)’ software was used
in Ref. [13] to calculate the flammable gas generation, migra-
tion, and combustion risk within the containment to calculate
the number of PARs need in a large Dry PWR containment in
order to prevent significant flammable gas combustion
events. CFD has been used by Ref. [14] to study the dynamic
behavior of a plate-type Areva FR-380 recombiner in a quies-
cent environment. The model was able to identify the phe-
nomenon of downward gas flow through the PAR metal casing
in the initial phase of the start-up period and to correlate the
magnitude and duration of this effect with the rate of increase
of hydrogen concentration in the environment [15]. Con-
structed and justified, a simple engineering thermo-hydraulic
model of hydrogen removal in the operation of a passive
autocatalytic recombiner based on the available experimental
data. The paper presented the application results of the model
as a part of contour industry codes RELAP, TRACE and COR-
SAR, intended, among other things, for carrying out multi-
factor and full-scale calculations of the dynamics of
emergency processes with the release of hydrogen into nu-
clear power plant premises. A passive containment cooling
system (PCCS) combined with hydrogen mitigation system is
suggested in Ref. [16] that will passively remove containment
heat load as well as mitigate hydrogen gas generated and
accumulated in the containment atmosphere during pro-
longed station blackout. They make use of atmospheric air as
ultimate heat sink to reject the PCCS heat, which in turn
transfers heat from the containment. In the proposed design a
finned vertical tube type PCCS system submersed in pool
water is considered with supply of pool water lasting three
days following which airflow cools PCCS tubes for long term.
The PCCS inlet flow path has a catalytic recombiner that is
effective during first few days should there be any hydrogen
generation and accumulation in the containment.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 8 5 8 4 e8 5 9 4
As a part of the analytical studies at BARC, India, Compu-
tational Fluid Dynamics (CFD) model [17] for simulating the
performance of PCRD in reactor containment has been
developed and validated against data from open literature.
The reaction kinetics data used for this model is specific to the
particular catalyst reported in open literature [18]. The present
study is aimed at detailed evaluation of the reaction kinetics
of the catalyst device developed at BARC, so that the analytical
model [17] can be fine-tuned for the India specific PCRD.
Experimental
Catalyst preparation
The PtePd over stainless steel wire gauze catalyst has been
prepared by electroless deposition method [12]. This method
involves chemical deposition of noble metals (Platinum and
Palladium) over the stainless-steel wire gauze in presence of a
reducing agent. The precursors used for Pt and Pd are Chlor-
oplatinic acid (Hindustan Platinum Private Limited, 39.8% Pt)
and palladium chloride (Hindustan Platinum Private Limited,
59.96% Pd) and reducing agent is formaldehyde (Thomas
Baker, 37e41%).
Catalyst characterization
Powder X-ray Diffraction has been used to assess the crys-
talline phase purity of deposited noble metals over the wire
gauge surface. The XRD patterns were recorded with Philips
analytical instrument with Ni filtered CueK-a radiation in the
scanning range of 10e70 two theta value. Surface
morphology and particle size of deposited noble metal nano-
particles has been studied using Scanning Electron Micro-
scopy (JEOLJSM-6360).
Catalytic activity evaluation
For generation of kinetics data for the prepared catalyst, the
H2 and O2 recombination reaction was performed under static
air condition at room temperature in a 40 L stainless steel
reactor Fig. 2[12]. The catalyst is hung inside the cylindrical
Fig. 2 e Schematic of experimental setup for kinetics study.
8587
reactor and the cylinder is pressurised to 1.1 bars with air.
During the start of each experiment, a known quantity of
hydrogen is injected into the reactor to attain a pre-decided
value of ~0.8e4.5% initial v/v hydrogen concentration for
various experiments.
The hydrogen concentration inside reactor is monitored
using thermal conductivity detector (TCD) based online
hydrogen monitor. The reaction being exothermic, the tem-
perature rise on the catalyst surface is recorded with the help
of two K-type thermocouples placed on the catalyst. The
change in concentration of hydrogen and the catalyst surface
temperature are recorded as functions of time.
From a series of experiments, data points have been
generated pertaining to variation of hydrogen concentration
and temperature with time [19]. The derivative plot of [H2] vs.
time provides for d [H2]/dt data for time ‘t’, at temperature ‘T’.
Substituting the values of [H2] and d [H2]/dt in Eq. (6) later, kT is
calculated for the respective temperature T.
For a typical experiment, where initial hydrogen concen-
tration was taken as 3.4% volume by volume, Fig. 3 depicts the
data used for reaction kinetics and activation energy calcu-
lations. The scatter plots in Fig. 3(a) represents change in
hydrogen concentration in moles/litre, Fig. 3(b) depicts the
change in temperature with respect to time and the derivative
plot -d [H2]/dt in moles/litre/sec. corresponding to rate of re-
action, with time t is depicted in Fig. 3(c). For each set of data,
rate constant kT is calculated for that temperature T,
employing Eq. (6). The activation energy calculated from ln
(kT) vs 1/T plot is shown in Fig. 3(d).
Results and discussion
Catalysts preparation
The catalyst is prepared using formaldehyde (Thomas Baker,
37e41%) as reducing agent with chloroplatinic acid (Hindustan
Platinum Private Limited, 39.8% Pt) and palladium chloride
(Hindustan Platinum Private Limited, 59.96% Pd) as noble metal
precursors and SS-304 wire gauze of wire diameter of 0.125 mm
and of 80 mesh number as a substrate for deposition [12,20].
The coating process employed is based on the following
8588 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 8 5 8 4 e8 5 9 4

Fig. 3 e Hydrogen concentration (a), catalyst temperature (b), derivative plot of [H2] (c) with respect to time and ln (kT) vs 1/T
plot (d).

reactions with anodic oxidation of formaldehyde and cathodic

reduction of noble metal taking place at the metal support
surface, which has been pre-activated by acid etching [21].

HCHO þ H2 O / HCOOH þ 2Hþ þ 2e ; E ¼ 0:057 V (1)

or Pt2þ þ 2e / Pdð0Þ or Ptð0Þ ;

2þ
Pd
(2)
E ¼ 0:915 V ðPdÞ; 0:726 V ðPtÞ

Though reduction of noble metal is reported to take place

at enhanced rate at higher pH it also requires presence of
complexing agents like EDTA to prevent precipitation of metal
in solution itself. Considering these effects of pH, the elec-
troless deposition was carried out at pH 2e4. The rate of
coating is found to be moderate but does result in amorphous
black noble metal coating with good adherence. The method
of preparation of catalysts is described in detail in earlier
publication [12].

Catalyst characterization
X-ray diffraction
Fig. 4 shows the XRD pattern of wire gauge as well as the
catalyst. The XRD pattern of the catalyst when compared to
the SS wire gauge have additional peaks at ~40 , ~46 and ~67 ,
2Q values. These peaks correspond to Platinum (JCPDS No.04-
Fig. 4 e XRD pattern of SS wire gauge support and PtePt
catalyst.
0802) and palladium (JCPDS 46-1043). The average crystallite
size of noble metal particles determined by Scherrer equation
using 40 peak and it was found to be around 21 nm.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 8 5 8 4 e8 5 9 4
Fig. 5 e Scanning electron micrographs of (a) stainless steel
Wire gauze, (b) stainless steel Wire gauze after HCl etching
and (c) PtePd catalyst over wire gauge.
Scanning Electron Microscopy
Scanning electron microscopy was used to evaluate the
effect of the deposition on morphology of the wire gauze
surface along with morphological study of PtePd nano
particles over the wire gauze surface. Fig. 5(a) and b
shows the SEM images of pristine wire gauze and HCl
etched wire gauze. The pristine wire gauze exhibits a
smooth surface and the HCl etched wire gauze also shows
similar morphology. The surface morphology of the cata-
lyst sample is shown in Fig. 5(c). It shows near spherical
8589
agglomerates with size ranging from few tens of nm to
1 mm.
Evaluation of reaction kinetics
The rate of H2 and O2 recombination reaction has been found
to depend on various factors like initial hydrogen concentra-
tion, catalyst geometric area and the temperature of the
catalyst surface. All these parameters are also found to be
interlinked. Rate of reaction was evaluated by generating data
pertaining to change in hydrogen concentration, temperature
and reactor pressure in real time for the reaction.
H2 þ ½ O2 4H2 O (3)
The rate of the reaction at any instant in time can be
described by Eq. (4).
d½H2 
Rate ¼  ¼ kT :½H2 x :½O2 y (4)
dt
where, kT is rate constant at temperature T (Kelvin) and x and
y are the order of the reaction with respect to H2 and O2
respectively.
For 4% initial hydrogen concentration in the reactor, the
stoechiometric oxygen concentration required is 2%.
Compared to this, the oxygen concentration in air is 20%,
which is 10 times more than the stoechiometric require-
ment. Hence, it can be assumed that the rate is indepen-
dent of the oxygen concentration in the reactor. Thus,
the rate equation can be reduced to the form shown in
Eq. (5):
d½H2 
 ¼ kT :½H2 x (5)
dt
This equation is rearranged to Eq. (6) for Arrhenius plot
1 d½H2 
kT ¼ : (6)
½H2 x dt
Various researchers have reported the order of the reaction
to be pseudo first order [22e24]. For heterogeneous catalytic
oxidation of hydrogen, it has been reported that hydrogen has
a high adsorption probability even for the surfaces preoccu-
pied by the adsorbed oxygen. Based on these observations,
Warnatz et al. [25] and Hellsing et al. [26] have also reported
order of reaction to be one. Therefore, the activation energy of
the reaction has been calculated, taking order of reaction, i.e.
x, as 1.
Plots as shown in Fig. 3 are generated for various set of
experiments involving different initial hydrogen concentra-
tions. Fig. 6 shows catalytic activity data obtained for catalyst
for initial hydrogen concentration ranging from 2.5 to 4%
in air.
One aspect observed is that the rate of reaction is strongly
dependent on initial concentration of hydrogen. As hydrogen
is injected into the reactor it starts reacting, with oxygen,
spontaneously on the catalyst surface and exothermicity of
the reaction leads to a sharp rise in temperature on the cata-
lyst surface, which in turn enhances the reaction rate further.
During the complete process the gas mixture and reactor
wall temperature are found to remain close to ambient con-
ditions. The catalyst temperature also comes down fast as the
8590 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 8 5 8 4 e8 5 9 4
reaction rate subsides with decreasing hydrogen concentra-
tion in the reactor vessel. This clearly indicates the usefulness
of stainless steel wire gauze support in terms of effective
dissipation of generated reaction heat. ln (kT) vs 1/T data ob-
tained from various set of experiments is plotted in Fig. 7. The
activation energy obtained from the above experiments is
found be in the range of 18.1 kJ/mol while the intercept
signifying pre-exponential factor is 0.76.
The kinetics for oxidation of hydrogen has been reported in
detail by various researchers. The gas phase oxidation process
is hindered by large activation energy in the range of
a tion of hydrogen and oxygen exhibit activation energy for
b affect of parallel channels on the kinetics of the recombina-
c In place of the support for hanging a single catalyst plate, new
Fig. 6 e Hydrogen concentration (a), Catalyst temperature
(b), Derivative plot of [H2 (c) with respect to time.
109e150 kJ/mol [27]. Compared to this surface assisted het-
erogeneous reaction has been reported to take place through
considerably lower activation energy barrier. The extent of
this barrier depends on the pathway followed.
Two of the prominent approaches are based on reaction
between adsorbed oxygen with either the gaseous hydrogen
or the dissociated hydrogen atom. The first mechanism as
discussed by Clyne [28] involving two step reaction based on
[O] þ H2 4 OH þ H and H2 þ OH 4 H2O þ H, exhibiting acti-
vation energy requirements of 25 kJ/mol. Since the activation
energy for these alternate paths exceeds the activation energy
data obtained from our experiments by large margin, the
feasibility for their occurrence is very low. Compared with
this, the reaction mechanisms based on dissociative adsorp-
various reaction steps in the range of 11.5 and 17.5 kJ/mol.
Hence it can be implied that the H2 þ O2 4 H2O reaction on the
present set of catalysts follows the similar pathway, based on
dissociative adsorption of both hydrogen and oxygen, fol-
lowed by combination of adsorbed species.
Study of channel effect on the kinetics
After evaluation of the reaction kinetics for the catalyst used
in PCRD, the next step is to investigate the behaviour of the
PCRD as a whole. The same is important to understand the
tion reaction. Here it is worth noting that the final surface
reaction taking place on the catalyst surface is one of the
many steps preceding and succeeding the same. The phe-
nomena of hydrogen and oxygen transport towards the
catalyst surface and the product water vapour away from the
catalyst surface by the virtue of diffusion and convection is
different for a bare catalyst as compared to a stack of parallel
channels of these catalyst plates. The estimation of overall
reaction kinetics for the device as a whole is approximated by
the single step Arrhenius equation.
For generation of reaction kinetics data of parallel channels
of catalyst plates, the set up shown in Fig. 2 has been modified.
catalyst holder was designed and fabricated to accommodate
four catalyst plates of the dimensions 50 mm  160 mm. The
Stainless steel assembly made for the same is shown in Fig. 8.
It has four parallel slots of 2.5 mm width so as to accommo-
date the catalyst plates of the SS wire gauze as well as cordi-
erite substrate with a pitch of 10 mm. The plates can be
inserted from the top and rest on the bottom plate in
respective slots. Arrangement is provided to attach the ther-
mocouples for temperature monitoring of the catalyst surface.
The top flange of the reactor is also changed with the one
having feed through connections for four numbers of ther-
mocouples instead of two. These four thermocouples are used
for recording the temperature at different heights of central
channel out of the three channels between four catalyst
plates.
Similar to single plate experiments, data points have been
generated for a series of experiments involving different
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 8 5 8 4 e8 5 9 4 8591

Fig. 7 e ln (kT) vs 1/T plot for the single plate of catalyst.

initial hydrogen concentrations. Fig. 9 shows catalytic ac-
tivity data obtained for catalyst for initial hydrogen concen-
tration ranging from around 2.0 to 4.5% in air. The
temperatures at different heights of central channel were
averaged suitably to get the temperature value resulting from
the recombination reaction. The derivative plot of [H2] vs.
time provides for d [H2]/dt data for time ‘t’ and at tempera-
ture ‘T’. Substituting the values of [H2] and d [H2]/dt in Eq. (6),
kT is calculated for the respective temperature T. ln (kT) vs. 1/
T values obtained from various set of experiments are plotted

Fig. 8 e Schematic of Assembly for supporting four catalyst plates.

8592 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 8 5 8 4 e8 5 9 4

b Fig. 10 e ln (kT) vs 1/T plot for parallel channels

arrangement between four plates.

Fig. 9 e Hydrogen concentration (a), Catalyst temperature

c
(b), Derivative plot of [H2] (c) with respect to time for four
plate arrangement.

in Fig. 10. The activation energy for the parallel channels

arrangement obtained from the above experiments is found
be in the range 18.7 kJ/mol, while the intercept signifying pre-
exponential factor is 0.8.
One set of experiments was also carried out by blocking
the outer surface of the two corner plates with aluminium
foil so as to restrict the lateral diffusion of hydrogen from the
sides and forcing all the hydrogen movement towards the
catalyst surface from the bottom of the channels between
the plates. Fig. 11 shows data obtained for these experiments Fig. 11 e Hydrogen concentration (a), Catalyst temperature
for initial hydrogen concentration ranging from 1.5 to 4.0% in (b), Derivative plot of [H2] (c) with respect to time for four
air. The temperature averaging was done similar to the plates with corner plates blocked from outside.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 8 5 8 4 e8 5 9 4
Fig. 12 e ln (kT) vs 1/T plot for parallel channels
arrangement between four plates with corner plates
blocked from outside.
earlier case to get the temperature value resulting from the
recombination reaction. The derivative plot of [H2] was also
plotted similarly.
Similar to the above procedure, the values of [H2] and dH2/
dt were substituted in Eq. (6), to calculate the kT respective
temperature T. Fig. 12 shows the ln (kT) vs 1/T values obtained
from various set of experiments. The activation energy for the
parallel channels arrangement by blocking the outer surface
of the two corner plates with aluminium foil is found out to be
20.6 kJ/mol, while the intercept signifying pre-exponential
factor is 1.81.
Conclusion
Reaction kinetics for the indigenous catalyst developed for
PCRDs to be deployed in Indian NPPs has been studied by
carrying out various lab scale experiments on the same. The
behaviour of these catalyst plates, when stacked in parallel
inside the recombiner box, has also been evaluated by car-
rying out semi-engineering scale experiments. The activation
energy calculated for the recombination reaction on the single
catalyst plate is found to be in range 18.1 kJ/mol, while the
intercept signifying pre exponential factor is 0.76. This value is
in accordance with the values reported for similar catalyst in
open literature. For the parallel channels arrangement where
the sides are open, the activation energy is found be in the
similar range 18.7 kJ/mol, and pre exponential factor is 0.8.
This shows that for the central channel, there is an extra
resistance for the diffusion of hydrogen towards the central
plates. This is due to part of the hydrogen getting consumed
on the outer surface of the corner plates due to lateral diffu-
sion from sides. This deprives the central channel with free
availability of hydrogen causing the overall activation energy
to be slightly more. When the outer surface of the two corner
plates in the parallel channels arrangement is blocked, the
lateral diffusion of hydrogen from the sides is prohibited. This
8593
leads to inflow of hydrogen towards the central channels from
the bottom only. Hence, in this case the activation energy is
found out to be 20.6 kJ/mol, while the pre-exponential factor is
1.81. This Arrhenius equation approximation of the overall
phenomena occurring inside the parallel catalyst plates
channels of PCRD is significant for modelling PCRDs inside
containment geometry using CFD.
Acknowledgement
Contribution of Shri D S Saini, RRDPD, BARC, Mumbai for
modification and additions in the test setup for four plate
experiments is sincerely acknowledged.
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