Reduction of SO2 in a pulsed corona discharge reactor: nitrogen, oxygen and

hydrogen sulphur effect

B. Jaramillo-Sierra2, A. Mercado-Cabrera1, B. Rodriguez-Mendez2, R. Lopez-Callejas1,2 ,
S. R. Barocio1, R. Valencia-Alvarado1, R. Peña-Eguiluz1, A. Muñoz-Castro1, A. De la Piedad-Beneitez2.

1
Instituto Nacional de Investigaciones Nucleares, Plasma Physics Laboratory
AP 18-1027, 11801 México D. F., Mexico.
*e-mail: antonio.mercado@inin.gob.mx
2
Instituto Tecnológico de Toluca, AP 890, Toluca, México

Abstract: Chemical processes of reduction and oxidation are studied using a non-thermal plasma, generated by a
coaxial pulsed corona discharge. A reduced numerical model is developed including the main chemical process in
sulphur dioxide removal from nitrogen, oxygen and hydrogen sulphide mixtures. SO2 decomposition experiments are
then performed in order to validate the numerical predictions of the model and to analyze the influence of separate
mixtures on the SO2 removal. The oxidation process is found to be the main path for SO2 removal and it turns out to be
enhanced by low quantities of moisture. Sulphur dioxide removal efficiencies in the order of 99% have been achieved
with the oxidation process.

Keywords: non-thermal plasma process, environmental applications, corona discharges.

1. Introduction the reduction process can successfully recover the

Sulphur dioxide (SO2) is one of the pollutants which
cause acid rain. The main sources of sulphur emission are
coal burning power plants, oil refineries, natural gas
purification plants and, generally, all activities concerning
the combustion of sulphur containing fuels. Sulphur
dioxide presents a low oxidation rate in environmental
conditions and tends to hover over the surroundings of
industrial plants and buildings to diffuse later into the
clouds and, finally, to precipitate itself as acid rain.
Conventional technologies have been used for SO2
removal on the basis of calcium carbonate although with
great amounts of calcium sulfate produced as waste [1].
Non-thermal plasma process can be used in order to
stimulate de oxidation of SO2 into SO3 and, afterwards,
eliminate the SO3 in the form of sulphuric acid. The latter
stage can be accomplished during the same plasma
process by in situ moisture addition. An additional
advantage of this non-thermal plasma process is the
capability of simultaneously treating different pollutant
gases, for example, SO2, NOx and hydrogen sulphide
(H2S). Electron beams, dielectric barrier discharges and
corona discharges are some applicable non-thermal
plasma sources. A relevant one is a pulsed corona
discharge (PCD) which can be used as an effective means
to oxidize SO2 into SO3 and, in this way, cleanse and
exhaust the gas, away from its hazardous sulphur
compounds [2].
The oxidation process is a path to SO2 removal while
sulphur. We have tried both chemical process using a µs
pulsed corona discharge without adding secondary
compounds to the mixture, in order to keep the technique
simple and avoid the formation of by-products. Thus, a
nitrogen-sulphur dioxide mixture was selected. As a first
case we increased the nitrogen concentration up to about
75% vol. For a second case, the nitrogen quantity was
substituted with hydrogen sulphide and, finally, we tried
with oxygen. For the second case, a chemical reduction
has been attempted by adding some hydrogen sulphur to
the corona discharge in order to verify an enhancement of
Claus' reaction [3]:
2 H 2 S + SO2 → 3S + 2 H 2 O
2. Description of the experimental setup
A typical coaxial wire within a Pyrex tube enabled the
generation of the corona discharge. The internal electrode
consisted of a stainless steel rod while the external
electrode was formed by a metallic mesh. The corona
reactor is showed in Fig. 1. The Pyrex tube was 9 mm
thick and 350 mm long. The diameter of the concentric
stainless steel rod was 3 mm. The gas gap was about 3
mm. A positive polarity pulsed voltage was applied to the
central rod and the metallic mesh was kept grounded. The
effective discharge volume was ~ 20 cm3.
The gas was supplied by pressurized cylinders. The SO2
content of the gas was varied throughout the experiment
by diluting its concentration using several cylinders with
N2, O2 and H2S. Two gas temperature levels were 2000 gas analyzer as well as a 30 m column gas
maintained, around 284 K and 296 K, throughout the chromatograph coupled to a mass detector. The carrier gas
experiment. was helium at a 99.995 % purity. An STD 1.0 l/min flow
A synthetic mixture containing 200 µmol/mol of SO2 was maintained permanently.
balanced in N2 was diluted separately with nitrogen,
oxygen and hydrogen sulphur and treated by the corona
discharge. Moisture (<3%) was added in order to enhance
the sulphur dioxide removal.

Fig. 2 Typical waveform of pulse voltage and current in

the plasma reactor

Fig. 1 Corona discharge generation system

The high voltage pulse power supply has been presented

previously in [4, 5]. It can continuously generate output
pulses with a peak voltage of 25 kV and a 0–30 µs width.
The pulse repetition rate is 50–2000 Hz. Both pulse
voltage and current waveforms are shown in Fig. 2. The
power transferred to the reactor was determined by
integrating the voltage-current characteristic.

The discharge voltage and current were measured so to

determine the pulse energy added to the gas flow. To this
purpose, a Tektronics P6015A 1:1000 probe, a 1.0 V/A
0.1–1.0 W transformer from Pearson Electronics Inc. and
a Tektronics TDS320 digital oscilloscope were used. By
multiplying the discharge voltage by the current pulse
values, we obtained the pulse power, as seen in Fig. 3.
The energy delivered to the polluted gas has been
obtained by integrating the discharge power over the
duration of the pulse. Provided that the secondary
streamers were, initially, not clearly identified (Fig. 3), we
considered the integration range as the whole pulse
duration time.
In the present work, the electrical energy input to the gas
was varied by changing the applied voltage. The
repetition frequency was constant and the pulse width was
a function of the applied voltage. A specific energy
deposited per pulse was equal to 5 x 10-5 – 4 x 10-4 J cm−3
and increased with the gas temperature.
The electric energy in the form of 10 and 15 kV pulses
at 500 Hz was applied to the central rod for approximately
6 min. The gas was monitored by means of a Sensonic
Fig. 3 Waveform of pulse power and energy in the plasma
reactor
3. Numerical Model
A theoretical study built around the group of reactions
that take place during the main SO2 removal process and
its interaction with oxygen and hydrogen sulphur was
developed. This 0-D chemical kinetics model took into
consideration the amount of power supplied to the flow
gas in the corona discharge reactor, calculated
experimentally as previously shown. The model consist
of two stages, the first one takes in account the electron –
molecule interactions present in the formation of radicals.
On the second stage, the radical–molecule interaction is
incorporated. We have considered about 190 reactions [1,
6-8] and 42 species such as: electron (e), ion positive
(O2+), atoms (O, N, H, S), molecules (O3, O2, NO2, NO,
NO3, N2, N2O, N2O3, N2O4, N2O5, SO2, SO3, SO, HN,
HO, HO2, H2O2, HNO, HNO2, H2, H2O, HNO3, HO2NO2,
HSO3, H2SO4, HSO2, H2S, HS, HSO) atoms and
molecules electronically excited [O(1D), O2(1∑g+), O(1S),
N(2D), N(2P), O2(a1∆g), N2(A3∑u+)].

The time density evolution of ni is given by

dni M ⎡ vl ⎤
= ∑ vl i ⎢k lf ∏ ni f i ⎥ (2)
dt l =1 ⎣ i ⎦

Where k lf is the direct reaction rate, k rl is the reverse

reaction rate for the reaction l, v lf i represents the
stoichiometric coefficient of species Ai in the direct
process for the reaction l. The variable vl i = +1 if a
species A is formed or vl i = −1 if it is decomposed in the Fig 5 N2: 9.9% (v/v); O2: 89 % (v/v); H2O: 1% (v/v) and
20 ppm SO2
reaction l. The system (2) can be solved using the
subroutine IVPAG from the International Mathematical
It is found in our calculations that increasing the oxygen
and Statistical Library (IMSL) in Fortran language,
content and decreasing the nitrogen one at same time,
selecting the multi–step Adams–Moulton algorithm for
enables to control the nitrogen oxide, favouring the
the stiff differential equation integrations.
elimination of sulphur dioxide. One can conclude then
that the sulphur dioxide presents a tendency to the
4. Results oxidization and not to the chemical reduction. If water is
A. Numerical modeling present, the oxidized sulphur reacts with it and sulphuric
Fig. 4 shows the results for a mixture containing, N2: 89% acid is formed, as it can be observed in the following
(v/v); O2: 9.9 % (v/v); H2O: 1% (v/v) and 180 ppm SO2 chemical reactions and in Fig. 5:
(~4.4 x1015 cm-3). In this mixture, the sulphur dioxide is
not completely eliminated; nevertheless, one can observe
SO2 + O + N 2 → SO3 + N 2
the different dissociation processes. Thus, in this case,
NxOy compounds are the main products formed. SO3 + H 2 O → H 2 SO4
OH + SO2 → HSO3
HSO3 + OH → H 2 SO4

With a view to verifying the Claus’s reaction in a non-

thermal plasma process, the sulphur dioxide removal was
enhanced employing the hydrogen sulphide as follows
from the Claus’s reaction:
2 H 2 S + SO2 → 3S + 2 H 2 O

Fig 4 N2: 89% (v/v); O2: 9.9 % (v/v); H2O: 1% (v/v) and
SO2: 180 ppm

Next, we increased the oxygen content while the nitrogen

and SO2 contents were progressively reduced. At this
point, the SO2 begun to be removed (Fig. 5).

Fig. 6 N2: 9.9% (v/v); O2: 89 % (v/v); H2O: 1% (v/v);

O2: 180 ppm; H2S: 10 ppm
The Claus process was carried out essentially at high
temperature albeit some catalyst was needed along the
reaction. This process was used to recover elemental
sulphur from hydrogen sulphide (H2S) in gases from oil
refineries [9].
In our calculations, we remark the partial oxidation of
hydrogen sulphide (Fig. 6) to form HSO according to the
reaction:
of the consumed power and of the gas analyzer response
time. Fig. 8 (a), (b) depicts the power level influence on
200 and 150 μmol of SO2 per mol, balanced in nitrogen,
respectively. One can distinguish two regions of each
power level, the first (I) is related to the direct removal by
the plasma process and the second (II) related to the
chemical reformation. As the SO2 concentration
decreases, both regions come closer. In nitrogen, the best
efficiency was established at around 16 %.

O + H 2 S → HSO + H
O + H 2 S → OH + HS
O + HS → OH + S

Likewise, the HSO formation causes the SO formation

and finally the SO2 re-conversion as can be observed in
Fig. 7:

HSO + O2 → HO2 + SO
HSO + O3 → OH + O2 + SO
SO + O2 → SO2 + O
SO + O3 → SO2 + O2 Fig 8 Experimental SO2 removal, N2 effect at 500 Hz

The highest efficiencies, close to 100%, were found

with gas mixtures diluted in oxygen. Fig. 9 (a), (b), (c)
and (d), displays the time concentration evolution. The
efficiency was increased by the consumed power and, as
the concentration declined, the efficiency was increased
(Fig 10).

Fig. 7 N2: 9.9% (v/v); O2: 89 % (v/v); H2O: 1% (v/v);

SO2: 20 ppm; H2S: 90 ppm

These results were obtained at 298 K where some traces

of sulphur were found, yellowing the translucent tubing
line. These results indicate that the first step of Claus's
reaction has been accomplished and the theoretical results
show that some water was also formed. An experimental
confirmation was achieved when water vapour was
condensed on the reactor walls.

B. Experimental results
Synthetic mixtures of 50, 100, 150 and 200 μmol of SO2
per mol were formed by the balance of nitrogen and
oxygen diluting the SO2 concentration. A pulsed voltage
was applied at a 500 Hz constant frequency, being the
residence time 1.2 s and the mixture flow rate in the
reactor 1.0 l/min. The results are presented as a function
Fig 9 Experimental SO2 removal, O2 effect at 500 Hz
Fig. 11 (a), (b), (c) and (d) exhibits the effect of 10, 50, 75
and 90 ppm, respectively, of H2S on a SO2–N2 mixture. In
all cases, a power raise entails a negative effect. The SO2
removal efficiency was diminished. The highest
efficiency barely reached 16%. Some studies are under
way aimed at understanding the effect of the temperature
on the process. It should be recalled that the above
described experiments have been performed at room
temperature. The content of catalyst is also being
analyzed.
Fig 10 SO2 removal efficiency, O2 effect at 500 Hz
Fig 11 Experimental SO2 removal; H2S effect at 500 Hz
5. Conclusions
Oxidation is the main path to the removal of sulphur
dioxide. Its highest efficiencies were found when
mixtures with oxygen were used. The chemical reduction
presented a rather poor efficiency. The hydrogen sulphide
at room temperature showed a slight effect on the SO2
removal. Further studies are being developed to
understand the high temperature behaviour of the gas
mixture.
Acknowledgment
This work was partially supported by CONACyT,
Mexico, under contract 060406.
References
[1] A. B. Saveliev, G. J. Pietsch, A. R. Murtazin and A.
Fried “SO2 removal from air with dielectric barrier
discharges” Plasma Sources Sci. Technol. 16 454–469
(2007).
[2] Alexander Fridman, “Plasma Chemistry”, Cambridge
University Press, (2008).
[3] Kasumov, F. B., Davydov A. A., Kerimov, I. Y., “The
Claus reaction. I: IR spectroscopy study of the reaction of
SO2 with the surface of an Sn-Mo oxide catalyst” Kinetics
and catalysis 32 (2) 1067-1072 (1991).
[4] Benjamín Gonzalo Rodríguez-Méndez, Régulo López-
Callejas, Rosendo Peña-Eguiluz, Member, IEEE, Antonio
Mercado-Cabrera, Raúl Valencia Alvarado, Samuel R.
Barocio, Anibal de la Piedad-Beneitez, Jorge S. Benítez-
Read, and Joel O. Pacheco-Sotelo, “Instrumentation for
Pulsed Corona Discharge Generation Applied to Water”
IEEE Trans. on Plasma Sci. 36 (1) 185-191 (2008).
[5] B. G. Rodríguez-Méndez, A. Mercado-Cabrera, R.
López-Callejas, R. Peña-Eguiluz, R. Valencia-Alvarado,
S. R. Barocio, A. de la Piedad-Beneitez, J. S. Benítez-
Read, and J. O. Pacheco-Sotelo, “AOP in Water by
Means of a DBD Conducted in a Coaxial Reactor” J. Adv.
Oxid.Technol. 11 84–90 (2008).
[6] J. J. Lowke, R. Morrow, “Theoretical analysis of
removal of oxides of sulphur and nitrogen in pulsed
operation of electrostatic precipitators” IEEE Trans. on
Plasma Sci. 23 661-672 (1995).
[7] R. Altkinson, R. A. Cox, J. N. Crowley, R. F.
Hampson Jr, R. G. Hynes, “Summary of Evaluated
Kinetic and Photochemical Data for Atmospheric
Chemistry Section I-Ox, HOx, NOx and SOx Reactions”
IUPAC Subcommittee on Gas Kinetic Data Evaluation for
Atmospheric Chemistry (2006).
[8] Atkinson R., Baulch D. L., Cox R. A., Crowley J. N.,
Hampson R. F., Hynes R. G., Jenkin M. E., Rossi M. J.
“Evaluated Kinetics and Photochemical data for
atmospheric chemistry. Vol I gas phase reactions of Ox,
HOx, NOx and SOx species” Atmos. Chem. Phys. 4 1461-
1738 (2004).
[9] Gary, J. H., Handwerk, G. E. “Petroleum Refining
Technology and Economics” 2nd Edition (1984).