April 2011, Volume 2, No.

2
International Journal of Chemical and Environmental Engineering

Non-thermal plasma assisted decomposition of H2S

into H2 and S
E. Lingareddy1* V.M. Biju1 and Ch.Subrahmanyam2
1
Department of Chemistry, National Institute of Technology Trichy, Trichy 620 015
2
Department of Chemistry, Indian Institute of Technology Hyderabad, Yeddumailaram 502205
* Corresponding author: csubbu@iith.ac.in

Abstract
The direct decomposition of hydrogen sulfide into hydrogen and sulfur was studied in a dielectric barrier discharge plasma reactor
with an inner electrode made of a stainless steel rod that was later replaced with a modified sintered metal fibers to introduce catalyst
inside the plasma zone. The feasibility of DBD plasmolysis for the hydrogen production by H2S decomposition was assessed. Typical
results indicate that H2 selectivity is ~100% throughout the range of present study. The influence of several parameters like the
discharge gap between the electrodes, residence time of the gas in the discharge zone, the applied voltage and the effect of catalyst
have been studied to find the optimal process conditions.

Keywords— decomposition, hydrogen sulfide, plasma reactor

1. Introduction direction has been to develop low cost and

Hydrogen is currently needed in large quantities as a
chemical feedstock for the synthesis of chemicals like
ammonia, methanol, and in the hydrodesulphurization and
hydrocracking of petroleum products [1]. Oil refineries
use hydrogen for desulphurization of crude oil to remove
sulfur as hydrogen sulfide (H2S) to achieve lower
mandated sulfur levels. Hence, a cheaper source of
hydrogen would be beneficial, especially for oil
refineries. Steam reforming of natural gas has been the
conventional methods for the production of hydrogen,
however emission of CO2, one of the major green houses
into the atmosphere is not longer acceptable [2, 3]. On the
other hand, the byproduct of desulphurization, H2S is
toxic and flammable and on contact with oxygen forms
sulfur dioxide (SO2), which has a negative impact on
environment. The generation and emission of H2S into the
atmosphere represents one of the two primary sources of
acid rain [1-3]. The conventional method for H2S
removal is the Claus process, which produces sulfur and
water through a high temperature oxidation step followed
by a low temperature reduction step. The energy
consumption of this process is relatively high due to the
thermal step; however, the heat generated in the furnace
can be recycled and reused as steam for other
applications. Besides sulfur recovery limitations, major
disadvantage of the Claus process is that the valuable
product hydrogen (H2) is not recovered, but converted
into water [1-5]. Also, as the conversion is not 100%, tail
gases cleanup may exceed the monitory benefit of the
recovered sulfur. Hence, the focus of research in this
environmentally benign alternatives to the Claus process,
such as the direct decomposition of H2S into constituent
elements H2 and sulfur. However, the main difficulty in
achieving this goal is that the direct decomposition of H2S
into H2 and S is an endothermic reaction and is favorable
only at higher than 2000K. Direct decomposition of H2S
into H2 and S is particularly interesting as it involves
resource utilization, value from waste and energy
production. However, in all the methods tested for this
approach, the amount of input energy is more than 285 kJ/
mol H2 produced, which is the maximum theoretical
energy that can be derived from hydrogen [1]. It is worth
mentioning that during steam reforming of methane, the
input energy demand is around 346 kJ/mol; hence
research focusing on the development of alternate
methods is warranted [1-4]. The dissociation of H2S has
been studied by several techniques, including non-thermal
plasma (NTP), which is characterized by high electron
temperatures under ambient conditions [4-10]. Plasma
techniques provide the advantage by direct decomposition
of H2S into H2 and S under ambient conditions [11,12].
Recently, a dielectric barrier discharge (DBD) reactor
with inner electrode made of sintered metal fibers (SMF)
also functioning as the catalyst was reported. The
developed reactor showed promising performance during
the destruction of various VOCs [10]. The objective of
the present work is to investigate the feasibility of DBD
plasmolysis for direct decomposition of H2S. The present
study also aimed at optimization of reaction conditions
such as the discharge gap between the electrodes,
 residence time of the gas, the applied voltage and the
effect of catalyst to achieve H2 production under
energetically favorable conditions.
2. Material and Method
2.1 Catalyst materials
The catalyst preparation was done as described
elsewhere [10]. Sintered metal fiber filters (Southwest
Screens & Filters SA, Belgium) made of stainless steel
(hereafter denoted as SMF) (Cr 16-18; Ni 10-13; Mo 2-
2.5; C  0.01; Fe balance) in the form of a uniform pore
panel (0.29 mm thick, 80 % porosity, 675 g/m2 density)
were used as the inner electrode. The SMF consists of
thin uniform metal fibers with diameter ~ 20 μm and
porosity of ~ 80 wt%. For the deposition of 5 wt% CoOx
and MoOx the SMF was first oxidized at 600°C for 3 h,
followed by impregnation with desired concentration of
aqueous cobalt nitrate and molybdic acid respectively.
The impregnated filter was then dried at room
temperature and subjected to an electrical hot press
treatment to shape them in to cylindrical form and
calcined for 5h at 500°C.
2.2 DBD plasma reactor
The dielectric discharge was generated in a cylindrical
quartz tube with an inner diameter of 19 mm. Silver paste
painted on the outside of the quartz tube over a length of
10 cm as the outer electrode, whereas a stainless steel rod
or modified SMF was used as the inner electrode. The
diameter of inner electrode was varied to obtain discharge
gap between 1.5 and 3.5 mm. A high voltage alternating
current in the range of 12.5-27.5 kV. An oscilloscope
(Tektronix, TDS 3054) was used to measure the applied
voltage of the system with a 1000:1 high voltage probe
(Fluke 80 K-40HV). The charge Q was measured by
15
10
Charge (nC*1000)
5 respectively. The same trend continued with increasing
0 discharge gap the residence time is ~ 6.8 s compared to
-5
-10
-15
-10 -5 0 5
Voltage (kV)
Fig. 1. V-Q Lissajous figures for 1.5 mm discharge gap
measuring the voltage across a capacitor (1nF to 4nF)
connected in series to the ground electrode. The H2S gas
(40 vol%) was diluted with argon (Ar) to get desired
concentration and was introduced into the reactor through
a Teflon tube, whose concentration at the outlet of the
reactor was measured with a gas chromatograph equipped
with a capillary column and a TCD detector. Hydrogen
formed in the reactor was measured with an online gas
chromatograph and also with H2 analyzer (Siemens). The
conversion of H2S at each voltage was measured after 30
minutes. A V-Q Lissajous method was used to measure
the discharge power in the plasma reactor. These signals
were plotted to generate Lissajous figures as shown in
Fig.1. The power was measured by multiplying the area
of the Lissajous curve with frequency applied on the
system. The specific input energy (SIE- J/l) was
calculated by dividing the power with flow rate of the gas
in liter per second.
3. Results and discussion
3.1 H2S decomposition in DBD plasma reactor and
influence of discharge gap
The designed DBD reactor was initially tested for H2S
decomposition (40 vol% in Ar and 150 ml/min flow rate)
with conventional stainless steel rod as the inner electrode
and the results are presented in Fig. 2. The discharge gap
between electrodes was varied between 1.5 to 3.5 mm and
typical conversion results as a function of applied voltage
are presented in Fig. 2. The interesting observation is that
during the present study, hydrogen and sulfur are the only
products, which highlight the advantage of NTP
compared to conventional methods like Claus process,
where hydrogen is converted into water. As seen from
the Fig. 2, at any discharge gap, conversion of H2S
increased with increasing voltage. The selectivity to
hydrogen was always 100%, which is further confirmed
by a gas chromatograph. The reactor was weighed before
and after H2S decomposition to get the mass of sulfur,
from which mass balance was calculated, which was ~
100%. In the case of plasma reactors, it is known that
with the discharge gap has a strong influence as it
influences the number and behavior of microdischarges.
As seen from the Fig. 2, conversion increases with
increasing discharge gap. However, during the present
study, for example at 12.5 kV, conversion increased from
~ 2 % to ~8% for 1.5 and 3.5mm discharge gap,
the applied voltage. This is due to the fact that, at 3.5 mm
3.3 s at 1.5 mm discharge gap. This also confirms the
earlier observation that at higher residence time
decomposition of H2S is high [10].
10
88
 30

3.5 mm 3.3 Influence of the catalyst

2.5 mm

1. 5 mm
In order to understand the influence of the catalyst,
20 H2S decomposition was tested with modified SMF
catalytic electrodes and results were presented in Fig. 4. It
Conversion (%)

has been observed that the conversion is nearly the same

10
0 have little effect leads to the suggestion that the catalyst is
10 12.5 15 17.5 20 22.5
voltage (kV)
Fig.2. Influence of discharge gap and voltage on conversion of H2S
(40 % H2S and 150 ml/min flow rate).
3.2 Influence of flow rate on H2S conversion
In order to understand the influence of flow rate on
conversion of H2S, at 1.5 mm discharge gap flow rate was
varied from 25 to 50 ml/min corresponding residence
time was 20 s and 10 s and the results are presented in
Fig. 3, which presents the influence of applied voltage on
conversion. As seen from the Fig.3, conversion of H2S
increases with increasing the voltage. Higher conversion
is observed at high applied voltage. As seen, with 25 ml
flow rate, conversion was 47% at 12.5 kV, which
increased to around 85% at 27.5 kV. This may be due to
availability of more number of microdischarges that may
decompose H2S. In order to ensure this observation,
for each catalyst, especially after one hour, suggesting no
influence of the catalysts. A difference of 10 % was
observed between CoOx and MoOx catalytic electrodes
for initial conversion. The fact that the catalysts seem to
25 27.5 30
immediately poisoned by sulfur deposition due to
relatively high H2S concentration compared to the catalyst
amount present on SMF filter (5 wt.%). The reason for
the decrease in the conversion with time can also be
explained due to the sulfur deposition on the electrodes of
the reactor, which may alter the discharge behavior.
Finally, it may be concluded that inspite of good
performance reported in literature for these catalysts, they
showed no significant influence during H2S
decomposition.
60
CoOx/SMF
50
MoOx/SMF
SMF
40 SS
Conversion (%)

flow rate has been increased two times and as seen,

30
conversion decreased significantly. This may be due to
shorter residence times at higher flow rate. As seen from 20
Fig. 3, with increasing flow rate from 25 to 50 ml,
conversion decreased from 47 to 20% at 12.5 kV. 10
Likewise, at 27.5 kV, conversion decreased from 85 to
65% and throughout the range of the applied voltage, 0
similar behavior was observed. Hence high conversion 0 0.3 0.6 0.9 1.2
was observed at low flow rate and high applied voltage. SIE(kJ/l)

However, maintaining a low flow rate may not be Fig. 4. Influence of the catalyst on the performance of DBD reactor.
energetically favorable. One of the ways to decrease the
input energy is to either increase the discharge gap and/or As of today there is no commercial technology for the
to increase the flow rate. production of hydrogen from hydrogen sulfide. In the
conventional Claus process, hydrogen is converted into
100
water, whereas direct decomposition into hydrogen and
25 ml
90 50 ml sulfur are beneficial. One of the reasons could be the
80
severe reaction conditions like high operating temperature
(> 2000 K). Moreover, the cost of tail gases cleanup from
70
Claus plant can exceed the monitory value of sulfur
Converion, %

60 recovered due to stringent environmental regulations. The

50
catalytic processes have been limited, mainly due to
deactivation of the catalyst by sulfur. Information has
40
been reported, where none of the catalysts was
30 promising.. Among the several techniques tested for the
20 direct decomposition of hydrogen sulfide, Idemitsu Kosan
12 14 16 18 20 22 24 26 28
Hybrid (IKC) electrolysis process has been considered as
Voltage (kV)
feasible. It is based on absorption of H2S by FeCl3
Fig. 3. Influence of flow rate on the conversion (25 % H2S, 1.5 mm aqueous solution followed by electrolysis to generate
discharge gap). hydrogen and sulfur. IKC process consumes 3.6 kWh/m3

89
 H2, whereas, steam reforming of methane, the traditional
approach for hydrogen production demands still higher
energy of 4.3 kWh/m3 H2. Like-wise, 40 % conversion of
H2S by thermal decomposition can be achieved at
temperatures ~ 1500 K, which is equivalent to 2.76
kWh/m3 of H2. At this temperature considerable amount
of by-products were produced. Formation of pure sulfur
and hydrogen was observed only above 2273 K. The
practical limitation of this technique is the operating
conditions and separation of products at this temperature.
The main advantage of carrying out H2S decomposition in
the DBD reactor presented here is the direct
decomposition of H2S into H2 and S. Further studies are in
progress to optimize the reaction conditions.
4. Conclusions
The decomposition of H2S into its constituent
elements, hydrogen and sulfur, has been studied in a
dielectric barrier discharge reactor. The present study
investigated the feasibility and the effectiveness of the
DBD technique for H2S decomposition. It has been
observed that the discharge gap and gas residence time
has a strong influence on H2 production and increasing
input energy may lead to higher conversion. Typical
results showed that, 1.5 mm discharge gap demands high
energy compared to 3.5 mm, which may provide optimum
residence time and low input energy. The SMF
modification with a catalyst may not influence the
efficiency indicating that catalyst may not be active
probably due to the small quantity, which can be easily
poisoned due to sulfur.
ACKNOWLEDGMENT
CS and EL thank MNRE for the financial assistance.
CS also wants to thank Prof. A. Renken and L. Kiwi-
Minsker of EPFL, Lausanne Swiss for support.
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