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Chemical Engineering Journal 228 (2013) 10661073

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Chemical Engineering Journal


journal homepage: www.elsevier.com/locate/cej

Energy efciency in hydrogen sulde removal by non-thermal plasma


photolysis technique at atmospheric pressure
Li Huang a,b,, Lanyan Xia a, Wenbo Dong a, Huiqi Hou a
a
b

Department of Environmental Science and Engineering, Fudan University, Shanghai 200433, PR China
Department of Energy, Environmental and Chemical Engineering, Washington University in St. Louis, MO 63130, USA

h i g h l i g h t s


 A combined plasma and KrBr photolysis reactor was constructed to decompose H2S.
 Energy cost for each H2S as low as 26 eV/molecule was achieved.
 Both removal and energy efciency were inuenced by various operation parameters.
2

 The new technique is safe because the main products were H2O and SO4 .

a r t i c l e

i n f o

Article history:
Received 15 March 2013
Received in revised form 11 May 2013
Accepted 14 May 2013
Available online 22 May 2013
Keywords:
Dielectric barrier discharge plasma with
photolysis
UV
Hydrogen sulde
KrBr2 excimer
Energy efciency

a b s t r a c t
In this paper, a novel combined non-thermal plasma photolysis reactor was employed to decompose H2S
in gas stream at atmospheric pressure. The lling gas pressure, applied voltage, and inlet H2S concentration were altered with the aim to improve the energy efciency. High H2S removal efciency could be
achieved with sufcient but reasonable energy density deposited on gas stream. The energy consumption
per molecule of destructed H2S, 26 1.5 eV/molecule, was relatively low as compared with those values
reported for plasma reactor operated at non-vacuum pressures and diluted condition. Furthermore, the
H2S decomposition mechanism was proposed as direct electron attachment, radicals and excited species
attack and photo-dissociation based on byproducts analysis by GC and IC. The results revealed the potential for energy efcient destruction of H2S by combined plasma photolysis process.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Growing concern has been given to sulfur-containing odorous
compounds because of their regular occurrence in animal industry,
natural gas and electrical industry [1,2]. Although the concentrations of these compounds are usually lower than the acute toxic level, their adverse effects on air quality and public health are
unavoidable concerning their extremely low olfactory detection
threshold. Taking H2S as example, its odor threshold is as low as
0.47 ppb [3]. Although industries involving in odorous compounds
attempt to control the odorous efuents, odor reduction is always a
challenging issue because these compounds can trigger unpleasant
feeling even at very low concentration.

Corresponding author. Present address: Wadsworth Center, New York State


Department of Health, Albany 12201-0509, USA. Tel.: +1 518 474 8828, tel./fax: +86
21 65642293.
E-mail address: lihuang1981@gmail.com (L. Huang).
1385-8947/$ - see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2013.05.058

Alternative techniques for H2S removal include scrubbing,


adsorption, bio-ltration, thermal and catalytic oxidation, and
advanced oxidation processes (such as photocatalysis). Scrubbing
and adsorption are non-destructive techniques and therefore require further treatment, while thermal and catalytic oxidations are
high energy-consumption processes. Bio-ltration, despite of low
cost, is easily inuenced by many physical and chemical parameters
and in consequence unstable. Photocatalysis techniques demonstrate promising removal efciency. The problems of poisoning or
deactivation of catalyst by the accumulation of byproducts on surfaces constrain the industrial application. With recent development
of new-type UV light source, named microwave discharge electrodeless lamps, direct photolysis technique has also been extended to
H2S decomposition [4]. These new light sources feature with strong
UVVUV radiant power and long lifetime. However, most of these
light sources are still under laboratorial investigation and need further improvement especially in energy efciency.

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L. Huang et al. / Chemical Engineering Journal 228 (2013) 10661073

Studies have shown that dielectric barrier discharge (DBD) is


especially capable of decomposing various pollutant gases [5,6].
Huge amount of highly reactive species including energetic
electrons, atoms, and radicals are generated under high voltage electric elds in dielectric barrier discharge, all of which are capable of
attacking pollutants either directly or indirectly. Sulfur-containing
gases have been subjected to DBD treatment on experimental scale
and decent removal efciencies have been achieved [79]. Despite
the high removal efciency, this technique shows low energy efciency and in turn constrains its industrial application. In 2007,
our group proposed to ll up the inner barrier with halogen along
with rare gas so that VUVUV irradiation would be spontaneously
ignited when high voltage was applied [10]. The simultaneous photolysis and plasma treatment were found to favor both pollutant removal efciency and energy efciency. This work only
demonstrated a feasibility test on the idea of combined dielectric
barrier discharge and photolysis (CDBD). No systematic investigation on the inuence of operation parameters on pollutant removal
was given. To develop and advance this technique to industrial
application, more laboratory studies are required either to extend
the technique to other pollutant removal or to obtain the optimal
operation conditions.
In our previous work [11], we addressed the performance of H2S
removal by dielectric barrier plasma and UVVUV irradiation from
a CDBD reactor using I2 as halogen. Removal efciency higher than
90% could be reached at optimal test condition, meaning CDBD
technique offers an alternative for H2S abatement. The energy efciency, however, was still less than satisfactory for industrial operation. Here, we further improve our combined plasma photolysis
system with the purpose of enhancing the overall energy efciency
of the reactor. A major improvement was to replace iodine (I2) by
bromine (Br2) based on a comprehensive consideration of the
emission spectrum of excimer and the H2S absorption spectrum
in UV region. H2S removal efciency and energy efciency were
carefully evaluated as a function of lling gas composition, applied
voltage, and inlet H2S concentration. Additionally, the mechanism
for H2S decomposition under combined plasma photolysis treatment was proposed. Since this is the rst time we compare the performance of CDBD reactor with different halogen for the same

pollutant removal, we are able to provide some prospective on


the future development of this technique.

2. Materials and methods


2.1. Experimental setup
The experimental system, shown in Fig. 1, is similar to our previous work [11]. In brief, it consists of a continuous gas ow control
and distribution system, a CDBD reactor, a power supply and gas
sampling system. The CDBD reactor, cylindrical in shape, was oriented vertically with gas ow from bottom to top. Both inner barrier and outer barrier are made of quartz. In order to increase
energy efciency, the inner diameter of the outer barrier was
increased to 40 mm as compared with our previous work. The inner barrier was made up of two co-axial quartz tubes sealed at
the ends and lled with a mixture of Kr and Br2. It has an inner
diameter of 10 mm and outer diameter of 20 mm. Both of the inner
barrier and outer barrier are 200 mm in length. Thus, the total volume of CDBD was enlarged to 188.5 cm3. The inner electrode is a
stainless sheet tting tightly with the inner wall of the inner barrier. The outer electrode, a stainless steel band 4 mm in width, is
wrapped around the outer side of the outer barrier. The discharge
is driven by a homemade square wave high-voltage supply capable
of delivering voltage from 0 to 10 kV at xed frequency of 20 kHz.
The accurate power dissipated into the plasma was determined by
a high voltage probe and a digital oscilloscope (Tektronix).
The desired concentration of H2Sair gas mixture ranging from
0 to 150 mg m3 was generated by carefully adjusting H2S (99.9%,
Nanjing Mucop Nanfen Special Gas Co.) and air ow rate using
mass ow controllers. The premixed gas was then introduced into
CDBD reactor by tunable air blower. Before sampling, the whole
setup was allowed to run for 20 min to make sure steady state
had reached. In all experiments, gas was fed into the reactor at
atmospheric pressure and ambient temperature (295 2 K), and
the ow rate was xed at 0.471 L s1 unless otherwise stated. For
each experimental condition, we performed three independent
experiments. The averaged results are reported in the paper. The

Air blower
Exhaust
High voltage
power supply

Inner
electrode

Sampling/
Detection system

DBD reactor

Pressure
gauge

Gas cylinder H2S

Outer
electrode
Kr + Br2

Volume flowmeters

Fig. 1. Schematic diagram of the experimental setup for H2S removal.

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L. Huang et al. / Chemical Engineering Journal 228 (2013) 10661073

errors stated in the present work are statistical errors for a condence interval of 95%.

90

2.2. Analytical methods


The concentration of H2S was quantitatively measured by colorimetric method which had been described in detail in our previous
work [4]. In brief, H2S in the gas stream was absorbed by N,N-dimethyl-p-phenylenediamine solution in acidic medium, followed
by reacting with FeCl3 to form methylene blue. H2S concentration
was then determined by the absorbance at 665 nm according to
LambertBeer Law. The destruction and removal efciency of H2S
(gH2 S ) in CDBD reactor could be easily calculated from the following formula:

gH2 S %

Removal efficiency (%)

80
70
60
50
40
30

H2S for 133.3 Pa Br2+ 133.3 Pa Kr

20

H2S for 133.3 Pa Br2+ 1.33 kPa Kr


H2S for 133.3 Pa Br2 +13.3 kPa Kr

10

H2S for 133.3 Pa Br2+ 26.7 kPa Kr

Bare DBD

H2S for 2mg I 2 + 47 kPa Kr

-10

H2 Sinlet  H2 Soutlet
 100%
H2 Sinlet

20

40

60

80

100

120

140

[H2S] (mg m-3)

The overall performance of H2S removal by CDBD was further


evaluated in terms of specic energy density (SED, represents the
amount of energy deposited in per volume gas), absolute removal
amount (ARA, represents the quantity of target compound decomposed in unit second), energy yield (EY, represents the quantity of
odorous compound decomposed for a given energy) and energy
cost per molecule (EC, represents the energy necessary to remove
one molecule).

Fig. 2. H2S removal efciency and energy consumption as a function of Kr pressure


at various initial H2S concentration (PBr2 = 133.3 Pa, applied voltage = 7.5 kV).

e Kr ! Kr 2e

e Br2 ! Br Br

SED J=L P=1000  Q

Therefore, KrBr excimers are readily produced by a three-body


ionic recombination reaction or harpooning reaction:

ARA g=s H2 Sinlet  gH2 S  Q  103

Kr Br M ! KrBr M

Kr Br2 ! KrBr Br

EY g=kW h 3600  H2 Sinlet  gH2 S =SED

EC eV=molecule

SED
H2 Sinlet  H2 Soutlet  106  1:6  1019  N A =M H2 S

where P is the power dissipated in the plasma (in W), [H2S]inlet and
[H2S]outlet are the inlet and outlet concentrations of H2S (in
mg m3), Q is the gas ow rate (in m3 s1), MH2S is the molar weight
of H2S (in g/mol), NA is the Avogadro constant (6.02  1023 molecule/mol for ideal gas).
3. Results and discussion
3.1. Improvement of removal efciency and energy consumption by
simultaneous non-thermal discharge and UV irradiation
When high voltage is applied, plasmas are created not only
within the pollutant gas stream but also within the lling gases
(e.g. Kr, Br2) in the inner barrier. KrBr excimer formed from Kr
and Br2 mixture discharge had been frequently reported to generate intense narrow bandwidth ultraviolet irradiation, and therefore
KrBr excimer based light sources were widely used [12]. As shown
in Fig. 2, the simultaneous irradiation due to Kr and Br2 mixture
discharge, in addition to direct discharge, contributed to H2S removal in our device. The enhancement of H2S removal efciency
turned signicant when H2S concentration was higher than
40 mg m3. With the addition of 133.3 Pa Kr and 133.3 Pa Br2 in inner barrier, H2S removal efciency jumped from 16.9% to 65.5% at
inlet H2S concentration of 110 mg m3, while the energy required
to remove single H2S molecule decreased from 106.7 27.5 eV to
26.0 1.5 eV. The energy efciency was therefore signicantly
improved.
Under the attack of high-energy electrons, Kr and Br2 are either
excited or ionized [12].

e Kr ! Kr e

where e represents for high-energy electron and M represents


anything that can serve as collisional third partner such as ion,
atom, excited molecule, and buffer gas.
The emissions from CDBD device, as recorded by a vacuumultraviolet spectrometer (American Acton Research Corporation
VM-505) coupled to a photomultiplier tube with sodium salicylate
uorescent coating, consisted of 80.2% 207-nm irradiation, 2.1%
222-nm irradiation, 5.4% 228-nm irradiation, and 12.3% 291-nm
irradiation. The 207-nm, 222-nm and 228-nm irradiations are in
good accordance with the characteristic emissions of KrBr excimer
due to B1/2 ? X1/2, C3/2 ? A3/2, and B1/2 ? A1/2 transitions, proving
the generation of KrBr excimer during dielectric barrier discharge.
The small amount of 291-nm irradiation came from Br excimer
relaxation to its ground state.

Kr Br2 ! Kr Br2

Br2 ! Br Br UV radiation 291 nm

With respect to the absorption cross sections of H2S [13], the UV


irradiation from excimers, in addition to direct electron attack,
contributed to the decomposition of H2S. In our previous work,
the lling of 47 kPa Kr and 2 mg I2 mixture was also found to enhance the removal efciency of H2S [11]. Since the inner diameter
of the outer barrier was increased in this study, we could not compare current data with our previous results directly. In order to
evaluate the importance of the type of lling compounds, we selectively tested H2S removal efciency at initial concentration of
110.0 mg m3 using 47 kPa Kr and 2 mg I2 mixture as inner barrier
ller (applied voltage was 7.5 kV and ow rate was 0.471 L s1)
(see Fig. 2). The removal efciency of 40.5% was far lower than that
obtained in this study by using 133.3 Pa Kr and 133.3 Pa Br2. The
signicant increase of H2S removal efciency in the presence of
Kr and Br2 might be related to the absorption spectrum of H2S.
H2S molecule has a broad absorption band ranging from 160
260 nm with peak centered at 195 nm. The emission lines of 207,

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L. Huang et al. / Chemical Engineering Journal 228 (2013) 10661073

222, and 228 nm originated from KrBr lie perfectly in this absorption band. Taking into account the absorption cross section of H2S
at 207 nm is four times larger than that at 183 nm [13], it is fairly
reasonable that a better H2S removal efciency and in consequence
a better energy efciency are achieved by addition of 133.3 Pa Kr
and 133.3 Pa Br2 in inner barrier.

molecule [14]. Even though our previous combined silent discharge and photolysis study to some extent improved the energy
utilization in non-thermal plasma treatment, energy consumption
at optimal condition was still 74 5.3 eV/molecule [11]. Similar or
better energy consumption was only reported by Cox et al. [15]
achieved at low pressure and John et al. [16] at high H2S concentration. According to literature, the cross sections for dissociative
electron attachment for H2S peaked at 2.2 and 9.0 eV with value
of 1.8  1018 and 4.8  1019 cm2 [17]. Although the ignition of
KrBr excimer consumes some input power, the 207-nm and
228-nm radiations from KrBr excimer would contribute to the photodissociation of H2S in return considering the absorption cross
sections of H2S at 207 nm and 228 nm are on the orders of magnitude of 10191018 cm2 mol1 [13].

3.2. Inlet H2S concentration effect


Fig. 2 also showed the evolution of H2S removal efciency as a
function of inlet H2S concentration. Unlike using I2 as inner barrier
lling gas, H2S removal efciency only dropped slightly with
increasing inlet H2S concentration when employing Br2 as lling
gas. The removal efciency of H2S decreased from 86.6% to 65.5%
when inlet H2S concentration increased from 12.6 to 115.4 mg m3
with inner barrier lled with 133.3 Pa Br2 and 133.3 Pa Kr. Both active species (electrons, radicals and ions) attack and UV photodissociation induced H2S removal from gas stream in CDBD. For a
given applied voltage and gas ow rate, the density and energy
of primary charged particles, radicals, electrons, and photons were
constant. With the increase of inlet H2S concentration, the averaged number of charged particles, radicals, electrons and photons
that was able to attack each H2S molecule reduced.
It is noteworthy that H2S removal efciency tends to be stable
when inlet H2S concentration exceeds 80 mg m3 with Br2 as inner
barrier lling gas. This is pretty exciting from the energy consumption point of view. Table 1 summarizes the absolute removal
amount (ARA), energy yield (EY), and energy cost (EC) information
at each tested experimental condition. Apparently, EC drops dramatically with increasing inlet H2S concentration. Energy cost for
each H2S molecule is as low as 26.0 1.5 eV/molecule at inlet
H2S concentration of 115.4 mg m3. Despite the extensive study
on H2S decomposition in non-thermal plasma in the past few decades, the energy consumption for low concentration H2S treatment
in air at atmospheric pressure is far from acceptable for commercial application. Typical energy consumption for low concentration
H2S conversion in pulsed corona discharge reactors is over 100 eV/

3.3. Inuence of lling gases pressure


In light of previous investigations on DBD driven excimer light
sources [18], the lling gases pressure and ratio have substantial
inuence on excimer emission intensity. To check the potential
inuence of lling gas on H2S removal efciency and energy efciency, the pressures of Br2 and Kr pressure inside inner barrier
were varied.
3.3.1. Br2 pressure effect
Shown in Fig. 3 were H2S removal efciencies obtained when
the inner barrier was lled with 66.7, 133.3, 266.7 and 666.7 Pa
Br2 respectively. The applied voltage was xed at 7.5 kV and
133.3 Pa Kr was served as rare gas in inner barrier. Similar trends
were obtained for inner barrier lled with 66.7 and 133.3 Pa Br2.
A gradual decrease of removal efciency with inlet H2S concentration was observed. There were no discernible differences in either
removal efciency or energy efciency between these two Br2
pressures at the inlet H2S concentration range studied. However,
further increase of Br2 pressure led to a drop in removal efciency
and a corresponding increase in energy cost, as presented in Table
2. A similar trend of Br2 pressure inuence on DBD driven KrBr

Table 1
Energy utilization at Kr pressure.
Inner barrier lling gases

Concentration (mg m3)

g (%)

133.3 Pa Br2 + 133.3 Pa Kr

12.6
22.2
60.0
80.8
94.9
115.4

86.6 4.2
83.8 5.6
75.3 5.1
68.7 4.6
67.5 3.3
65.5 3.7

133.3 Pa Br2 + 1.33 kPa Kr

14.0
38.1
56.8
97.3
111.6

133.3 Pa Br2 + 13.3 kPa Kr

ARA (g s1)

EY (mg kW h1)

EC (eV/mol)

5.14 0.25
8.76 0.59
21.3 1.44
26.2 1.75
30.2 1.48
35.6 2.01

207.5 10.1
353.8 23.6
859.2 58.2
1055.7 70.7
1218.3 59.6
1437.5 81.2

180.1 8.8
105.6 7.1
43.5 2.4
35.4 1.5
30.7 1.6
26.0 1.5

78.1 4.1
69.4 4.3
66.5 3.2
62.7 3.5
60.3 3.1

5.15 0.27
12.45 0.77
17.79 0.86
28.73 1.60
31.70 1.63

207.9 10.9
502.9 31.2
718.4 34.6
1160.3 64.8
1279.8 65.8

179.7 9.5
74.3 4.6
52.0 2.5
32.2 1.8
29.2 1.5

15.3
41.2
70.2
108.2
145.3

83.4 3.9
59.0 4.5
55.1 4.2
49.6 3.9
42.5 3.2

6.01 0.28
11.45 0.87
18.22 1.39
25.28 1.99
29.09 2.19

242.7 11.3
462.3 35.3
735.6 56.1
1020.7 80.3
1174.4 88.4

154.0 7.2
80.8 6.2
50.8 3.9
36.6 2.9
31.8 2.4

133.3 Pa Br2 + 26.7 kPa Kr

7.47
23.5
48.9
73.4
113.7

87.5 3.6
66.3 4.4
45.6 4.2
39.7 3.8
35.5 3.0

3.08 0.13
7.34 0.49
10.50 0.97
13.72 1.31
19.01 1.61

124.3 5.1
296.3 19.7
424.1 39.1
554.2 53.0
767.6 64.9

300.6 12.4
126.1 8.4
88.1 8.2
67.4 6.5
48.7 4.1

Bare DBD

3.6
27.1
37.1
54.0
109.0

76.2 3.2
65.1 4.1
52.6 5.0
34.3 4.2
16.9 4.1

1.29 0.05
8.31 0.52
9.19 0.87
8.72 1.07
8.68 2.10

52.2 2.2
335.5 21.1
371.1 35.3
352.3 43.1
350.3 85.0

716.3 30.1
111.4 7.0
100.7 9.7
106.1 13.2
106.7 27.5

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L. Huang et al. / Chemical Engineering Journal 228 (2013) 10661073

7.5 kV. As shown in Fig. 2, H2S removal efciencies obtained with


the addition of 133.3 Pa Kr were the highest among all Kr pressures
tested. The discrepancies in removal efciency were especially signicant at inlet H2S concentration higher than 45 mg m3. H2S removal efciencies were 16.9%, 65.5%, 60.3%, 42.5%, and 35.5%
respectively at inlet H2S concentration around 115.0 mg m3 with
addition of 0, 133.3, 1330, 13300, and 26700 Pa Kr. Different from
our previous work [10], no adverse effect was observed over all the
reaction conditions tested as compared with bare DBD treatment.
As a rare gas, Kr pressure would impact the emission intensities
from KrBr2 mixture driven by DBD in multiple ways. It is an
important component for the generation of KrBr according to
Eqs. (1), (2), (4), and (5). Many researchers have reported the typical trend of KrBr emission intensity with Kr pressure under
dielectric barrier discharge: a gradual increase with Kr pressure
up to 2  104 Pa and a gradual decrease with further increase of
Kr pressure [18,19]. The number of KrBr excimer increased as a result of increasing ionic krypton at low Kr partial pressure, while
more KrBr were quenched by krypton atoms to form triatomic
species at high pressure. In this study, however, H2S removal efciency peaked at Kr pressure of 133.3 Pa and total lling gas pressure of 266.6 Pa. It demonstrated a decay trend with the further
increase of Kr pressure. A possible explanation for this phenomenon was that the increase of lling gases in the inner barrier led
to more energy consumption in the generation of KrBr excimer
in inner barrier and a corresponding decrease in energy directly
dissipated on the pollutants containing gas stream.
The inuence of lling gas pressure on energy efciency (see
Table 3) was in analogy with its inuence on H2S removal efciency. It was because H2S removal efciency was the only factor
that had impact on energy cost at given applied voltage, gas ow
rate, and inlet H2S concentration.

Removal efficiency (%)

100

80

60

40
H2S for 133.3 Pa Kr + 66.7 Pa Br2
H2S for 133.3 Pa Kr + 133.3 Pa Br2

20

H2S for 133.3 Pa Kr + 266.7 Pa Br2


H2S for 133.3 Pa Kr + 666.7 Pa Br2

0
0

20

40

60

80

100

120

[H2S] (mg m-3)


Fig. 3. H2S removal efciency and energy consumption at various Br2 pressure
when applied voltage was 7.5 kV.

excimer lamp in terms of emission power was reported by Avdeev


et al. [18]. Comparing the emission of KrBr2 mixture under discharge and the absorption spectrum of H2S, we may easily nd
out only the emissions due to KrBr excimer contribute to the photodissociation of H2S. As indicated in Eqs. (3)(5), Br2 plays a crucial role in the formation of KrBr excimer. Total radiation power
of KrBr initially increased with Br2 pressure. However, the increase of Br2 pressure also increase the nonradiative decay of KrBrdue to the collisions of KrBr with bromine molecules/atoms and
other neutral particles.

KrBr Br2 Br ! Kr Br Br2 Br

8
3.4. Applied voltage effect

The total radiation power of KrBr began to decrease with Br2


pressure after achieving a maximum value.

Applied voltage is another predominant factor that may inuence H2S removal efciency due to its potential inuence on energy dissipation in the reactor. Fig. 4 presents the variation of
H2S removal efciency with applied voltage at inlet H2S concentration of 3.3 and 41.9 mg m3 respectively. H2S removal efciency

3.3.2. Kr pressure effect


The inuence of Kr pressure on H2S removal by CDBD was then
investigated at Br2 pressure of 133.33 Pa and applied voltage of
Table 2
Energy utilization at Br2 pressure.
Inner barrier lling gases

Concentration (mg m3)

g (%)

EY (mg kW h1)

EC (eV/mol)

66.7 Pa Br2 + 133.3 Pa Kr

1.62
3.30
41.9
55.0
96.8
107.3

99.1 0.9
96.3 3.8
88.6 6.1
76.4 4.9
64.8 3.1
63.2 4.4

ARA (g s1)
0.76 0.02
1.50 0.06
17.5 1.20
19.8 1.27
29.5 1.41
31.9 2.22

30.5 1.0
60.4 2.4
706.0 48.6
799.1 51.3
1192.9 57.1
1289.7 89.8

1223.9 25.9
618.3 24.4
52.9 3.7
46.8 3.0
31.3 1.5
29.0 2.0

133.3 Pa Br2 + 133.3 Pa Kr

12.6
22.2
60.0
80.8
94.9
115.4

86.6 4.2
83.8 5.6
75.3 5.1
68.7 4.6
67.5 3.3
65.5 3.7

5.14 0.25
8.76 0.59
21.3 1.44
26.2 1.75
30.2 1.48
35.6 2.01

207.5 10.1
353.8 23.6
859.2 58.2
1055.7 70.7
1218.3 59.6
1437.5 81.2

180.1 8.8
105.6 7.1
43.5 2.4
35.4 1.5
30.7 1.6
26.0 1.5

266.7 Pa Br2 + 133.3 Pa Kr

5.47
18.3
39.8
64.3
89.1
110.3

90.5 3.1
80.2 4.5
74.5 5.6
65.4 5.2
57.3 4.3
52.6 4.0

2.33 0.08
6.91 0.39
13.97 1.05
19.81 1.57
24.05 1.80
27.33 2.08

94.1 3.2
279.1 15.7
563.9 42.4
799.8 63.6
971.0 72.9
1103.4 83.9

396.9 13.6
133.9 7.5
66.3 5.0
46.7 3.7
38.5 2.9
33.9 2.6

666.7 Pa Br2 + 133.3 Pa Kr

10.8
25.3
54.9
78.4
97.5
116.7

82.3 4.8
76.1 5.7
62.7 5.3
55.2 4.7
49.6 5.1
45.9 3.9

4.19 0.24
9.07 0.68
16.21 1.37
20.38 1.74
22.78 2.34
25.23 2.14

169.0 9.9
366.2 27.4
654.7 55.3
823.1 70.1
919.7 94.6
1018.7 86.6

221.1 12.9
102.1 7.7
57.1 4.9
45.4 3.9
40.6 4.2
36.7 3.1

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L. Huang et al. / Chemical Engineering Journal 228 (2013) 10661073


Table 3
Energy utilization at different applied voltage.
Concentration
(mg m3)

Voltage (kV)

g (%)

SED (J L1)

3.3

3.6
4.8
6.0
7.5
9.0

57.9 4.8
81.1 4.2
89.3 3.7
96.3 3.2
99.4 0.6

74.1 1.9
109.0 2.7
142.1 3.6
189.3 4.7
231.0 5.8

0.90 0.07
1.26 0.07
1.39 0.06
1.50 0.05
1.54 0.04

92.8 7.7
88.4 4.6
74.7 3.1
60.4 2.0
51.1 1.28

402.7 33.6
422.6 21.9
500.5 20.8
618.3 20.6
730.8 18.3

41.9

3.6
4.8
6.0
7.5
9.0

35.6 4.6
63.2 5.9
86.6 5.4
88.7 6.1
99.6 0.4

74.1 1.9
109.0 2.7
142.1 3.6
189.3 4.7
231.0 5.8

4.04 0.52
7.18 0.67
9.83 0.61
10.06 0.69
11.31 0.28

724.5 93.6
874.8 81.7
919.2 57.3
706.0 48.6
650.5 16.3

51.6 6.8
42.7 4.0
40.7 2.5
52.9 3.7
57.4 1.4

EY (mg kW h1)

EC (eV/mol)

of collision between active species (electrons, ions and photons)


and H2S molecule. However, the input energy also increased significantly. The variation of energy efciency of CDBD exhibited the
combined effect of applied voltage on active species generation
and total energy input. In current research, the energy efciency
of CDBD reactor, indicated by EY and EC, dropped after the applied
voltage exceeded 7.5 kV.

100

Removal efficiency (%)

ARA (g s1)

80

60

3.5. Byproducts analysis and decomposition mechanism


40

20

-1

H2S at [H2S]0 = 41.9 mg L


-1

H2S at [H2S]0 = 3.3 mg L

0
3

Applied Voltage (kV)


Fig. 4. H2S removal efciency as a function of applied voltage at initial H2S
concentration of 3.3 and 41.9 mg m3 respectively (PKr = 133.3 Pa, PBr2 = 133.3 Pa).

increased monotonously with applied voltage. The increase was


more apparent when applied voltage altered in the 4.56.0 kV region. To initiate discharge, electric eld in the discharge gap high
enough to cause break down was required. Typical voltage needed
to establish plasma in barrier dielectric reactor operating under
atmospheric pressure was around several kV [20]. Once breakdown occurred, a large amount of microdischarges were formed
within the space between electrodes. Each individual microdischarge, in which active discharge species and energy dissipation
mainly accumulated, could be regarded as a miniature plasma
chemical reactor. Therefore, considerable H2S removal was
observed when applied voltage exceeded 4.5 kV. The increase of
applied voltage brought about an enhancement in the density of
microcharges. In the meanwhile, evidenced by vacuum-ultraviolet
spectroscopy, the UV emission intensity from the CDBD reactor increased with applied voltage either. As a result, H2S removal efciency increased with the applied voltage accordingly.
As illustrated in Table 3, absolute H2S removal amount exhibited similar trend as H2S removal efciency with applied voltage.
ARA was a function of removal efciency, inlet H2S concentration
and gas ow rate. Provided that gas ow rate was xed, ARA was
only inuenced by H2S removal efciency at given inlet H2S concentration. The variation of energy yield and energy cost with applied voltage turned out to be far more complicated. At low inlet
H2S concentration, most energy was consumed in the excitation
of plasma instead of the removal of target pollutant, leading to a
low energy yield and energy cost. Higher applied voltage did increase the density of microdischarge and consequently the chance

A major concern in CDBD application to H2S decomposition is


the secondary hazardous compounds production accompanying
the decomposition process. It is therefore necessary to perform
byproducts analysis to address the safety of current technique.
Moreover, the mechanisms for pollutant decomposition are still
under debate. The success of byproducts analysis might contribute
to a better understanding of removal mechanism under CDBD.
80.8 mg m3 H2S was continuously introduced into reactor at
ow rate of 0.471 L s1. The gases after CDBD treatment (applied
voltage was 7.5 kV) were harvested by a liquid nitrogen trap at
the downstream of reactor. After 30-min collection, the trapped
gases were warmed to room temperature and then subjected to
FT-IR analysis. The only discernible product in gas stream exiting
CDBD reactor was H2O, indicating extensive decomposition reaction of H2S took place. Based on previous literature reports and
experimental results, there were three predominant mechanisms
responsible for H2S decomposition.
3.5.1. Direct electron attack
According to Raos study [17], the cross sections for dissociative
electron attachment for H2S to form HS- demonstrated a peak at
2.2 eV with value of 1.8  1018 cm2. Considering most electrons
in dielectric barrier discharge possessed energy in the range of
010 eV, the probability for H2S dissociation into HS- due to direct
electron attack was extremely high.

H2 S e ! H HS

17

9


The appearance of a small amount of S was also expected as a


result of the direct electron attack of H2S. Since the cross sections
for dissociative electron attachment for H2S to form S were far
smaller than those to form HS [17], the concentration of S would
not accumulate to signicant level.

H2 S e ! H2 S

17

10

H2 S e ! 2H S

17

11

3.5.2. Reactions with electron-induced excited species and free


radicals
Taking into account the partial pressures of N2 and O2 in gas
stream, their direct collisions with electrons were inevitable. With

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L. Huang et al. / Chemical Engineering Journal 228 (2013) 10661073

respect to the electron energy distribution in dielectric barrier discharge, the major processes could be expressed as following
equations.

N2 e ! N2 A3 Ru e

21

12

O2 X 3 Rg e ! O2 2 Pu ! O 2 P O3 P 22

13

O2 e ! O2

14

21

These electronic excited species and radicals contributed to H2S


dissociation through either direct reactions with H2S or reactions
with fragments from H2S decomposition.

N2 A3 Ru H2 S ! N2 H HS 23
1

k 3:0  1010 cm3 molecule

s1

15

H2 S O3 P ! OH HS 24
1

k 2:2  1014 cm3 molecule

s1

16

1

s1

17

1

s1

18

HS O3 P ! OH S 24
k 1:6  1010 cm3 molecule
HS O2 ! OH SO 24
k < 4:0  1019 cm3 molecule

1

k 2:1  1012 cm3 molecule

S O2 ! SO O 25

s1
19

SO O2 ! SO2 O 25
1

k 7:6  1017 cm3 molecule

s1

20

SO2 O3 P M ! SO3 M 24


2

k 1:3  0:7  1031 cm3 molecule

s1

21

However, as indicated by FT-IR, no sulfur-containing gaseous


products were detected. This might be caused by the further reaction of SO3. Regarding the fast combination of H and OH radicals,
the presence of H2O in the reactor was unavoidable. It is very likely
that reaction occurred between SO3 and H2O. The foggy H2SO4
formed along with H2O vapor would later deposit on the wall of
the reactor. In order to prove the assumption, 100 mL deionized
water was used to rinse the wall of CDBD reactor. According to
IC analysis, the amount of S in the form of S(VI)(45.6 mg) in rinse
water accounts for 97% of the total decomposed S from H2S, meaning most decomposed S would nally convert to S(VI).

SO3 H2 O ! H2 SO4
reactor wall

H2 SO4 ! surface adsorbed H2 O; H2 SO4 ; SO2


4

22
23

S(VI) was the only detectable sulfur-containing species in gaseous and liquid products, indicating the high oxidation ability of
CDBD technique.
3.5.3. Dissociation by plasma-triggered KrBr radiation
The signicant promotion of H2S removal efciency in the presence of rare gas and halogen in inner barrier and lling gas pressure dependent H2S removal efciency had provided solid proofs
that plasma-triggered KrBr radiation contributed to H2S dissociation as well. The absorption cross sections of H2S in UV region have
been studied by many research groups [13,2628]. It was well accepted that H2S had a broad absorption in the 160260 nm region

with a peak at 195 nm. The characteristic emissions of KrBr can


readily cause HS cleavage when absorbed by H2S molecule.

H2 S hm ! H HS 29; 30

24

The subsequent oxidation of H and HS resembled those fragments originated from electron attack.

4. Prospectives of CDBD technique


By far, our group has investigated the removal efciency and
energy efciency for H2S removal from air stream by the dielectric
barrier discharge combined with either KrI photolysis [11] or
KrBr photolysis (this work) technique at atmospheric pressure.
Attractive performance has been achieved at optimal operation
condition. Energy cost for each H2S of 26 1.5 eV/molecule was
approaching the lowest energy cost ever reported for plasma reactor operated at non-vacuum pressures and diluted condition. It is
time to reect on the advantages and limitations of CDBD technique which may benet its further improvement and the eventual
industrial practice.
The target pollutant we selected was odorous inorganic compound H2S. Dielectric barrier discharge combined with KrBr2 photolysis showed predominant advantage over DBD combined KrI2
photolysis for H2S abatement both in removal efciency and
energy efciency. Regarding the experimental results, plasma-triggered excimer photodissociation, along with direct electron attack
and electron-induced excited species and free radicals reaction, led
to the decomposition of pollutants. 207-nm light was identied as
the dominant emission for KrBr2 mixture, while 183-nm light
dominated the emission from KrI2 mixture. 207-nm and 183nm photons, with energy of 6.01 and 6.79 eV respectively, were
capable of destroying most chemical pollutants. The higher photon
energy of 183-nm photon did not presumably bring about higher
removal efciency. On the contrary, H2S removal efciency by
DBD combined KrI2 photolysis was far lower than that by DBD
combined KrBr2 photolysis. One explanation was that the absorption cross section at 183 nm was lower than that at 207 nm. The
other non-negligible reason was that O2, as a major component
in the gas stream, competitively absorb radiations from excimer
with cross section on the order of magnitude of 1020 cm2 mol1
at 183 nm [31]. With part of radiation absorbed by O2, a decline
in direct photolysis of H2S could be expected. Compared with that
at 183 nm, the absorption cross section of O2 at 207 nm was four
orders of magnitude lower. Thus, most radiation would directly
interact with H2S molecule when H2S was subjected to DBD combined KrBr2 photolysis treatment.
The inuence of inner barrier lling gas pressure on the performance of CDBD was systematically investigated in this work as
well. The variations of H2S removal efciency with lling gas pressure were not only controlled by the inuence of lling gas pressures on KrBr excimer intensity. The optimal H2S removal
efciency and energy efciency were achieved when inner barrier
was lled with 133.3 Pa Br2 and 133.3 Pa Kr, indicating the pressure of lling gas may affect the energy dissipation between inner
barrier lling gas and pollutant gas stream as well.
It is noteworthy that the overall performance of CDBD technique may vary with different target pollutants because the removal efciency is highly dependent on the dissociative electron
collision cross sections and absorption cross sections of pollutants.
For each pollutant, a combined consideration of electric and optical
properties should be taken into account when designing the optimal CDBD setup. If necessary, a different combination of rare gases
and halogens, such as KrF2 and KrCl2, is also worthy a shot. More
laboratory-scale and pilot-scale studies dealing with different
group pollutants are in demand of with the purpose to improve

L. Huang et al. / Chemical Engineering Journal 228 (2013) 10661073

pollutant removal efciency and reduce energy cost for each pollutant in future.

5. Conclusions
In this paper, energy efciency of a combined dielectric barrier
discharge and photolysis reactor for H2S removal was carefully
evaluated. By lling inner electrode with Kr and Br2, high H2S removal efciency could be achieved with sufcient but reasonable
energy density deposited on gas stream. The energy consumption
per molecule of destructed H2S, 26 1.5 eV/molecule, was relatively low as compared with those values reported for plasma
reactor operated at non-vacuum pressures and diluted condition.
Moreover, we compared the performance of CDBD reactor with
different halogen for the same pollutant removal. The results revealed the potential for energy efcient destruction of H2S by combined plasma photolysis process.
Acknowledgments
This work was nancially supported by the Natural Science
Foundation of Shanghai. Dr. Huang would like to thank the innovative funding from Fudan University and the fellowship from Shanghai Tongji Gao Tingyao Environmental Science and Technology
Development Foundation.
References
[1] J. Zhu, L.D. Jacobson, Correlating microbes to major odorous compounds in
swine manure, J. Environ. Qual. 28 (1999) 737744.
[2] M.S. Legator, C.R. Singleton, D.L. Morris, D.L. Philips, Health effect from chronic
low-level exposure to hydrogen sulde, Arch. Environ. Health 56 (2001) 123.
[3] J.M.M. De Zwart, J.G. Keunen, C1-cycle of sulfur compounds, Biodegradation 3
(1992) 3759.
[4] L. Xia, D. Gu, J. Tan, W. Dong, H. Hou, Photolysis of low concentration H2S under
UV/VUV irradiation emitted from microwave discharge electrodeless lamps,
Chemosphere 71 (2008) 17741780.
[5] L. Xia, L. Huang, X. Shu, R. Zhang, W. Dong, H. Hou, Removal of ammonia from
gas streams with dielectric barrier discharge plasma, J. Hazard. Mater. 152
(2008) 113119.
[6] H. Kim, Nonthermal plasma processing for air-pollution control: a historical
review, current issues, and future prospects, Plasma Process. Polym. 1 (2004)
91110.
[7] A. Khacef, J.M. Cormier, Pulsed sub-microsecond dielectric barrier discharge
treatment of simulated glass manufacturing industry ue gas: removal of SO2
and NOx, J. Phys. D: Appl. Phys. 39 (2006) 10781083.
[8] C. Zhu, J. Lu, X. Wang, Q. Huang, L. Huang, J. Wang, Removal of carbon disulde
from gas streams using dielectric barrier discharge plasma coupled with MnO2
catalysis system, Plasma Chem. Plasma P 33 (2013) 569579.

1073

[9] C. Zhu, X. Wang, Q. Huang, L. Huang, J. Xie, C. Qing, T. Chen, Removal of gaseous
carbon bisulde using dielectric barrier discharge plasmas combined with TiO2
coated attapulgite catalyst, Chem. Eng. J. 225 (2013) 567573.
[10] H. Fang, H. Hou, L. Xia, X. Shu, R. Zhang, A combined plasma photolysis (CPP)
method for removal of CS2 from gas streams at atmospheric pressure,
Chemosphere 69 (2007) 17341739.
[11] L. Huang, L. Xia, X. Ge, H. Jing, W. Dong, H. Hou, Removal of H2S from gas
stream using combined plasma photolysis technique at atmospheric pressure,
Chemosphere 88 (2012) 229234.
[12] Ch.K. Rhodes, Excimer Lasers Topics in Applied Physics, Springer, Berlin, 1979.
pp. 8996.
[13] C.Y.R. Wu, F.Z. Chen, Temperature-dependent absorption cross sections of H2S
in the 160260 nm region, J. Quant. Spectrosc. RA 60 (1998) 1723.
[14] J. Jarrige, P. Vervisch, Decomposition of gaseous sulde compounds in air by
pulsed corona discharge, Plasma Chem. Plasma P 27 (2007) 241255.
[15] B.G. Cox, P.F. Clarke, B.B. Pruden, Economics of thermal dissociation of H2S to
produce hydrogen, Int J. Hydrogen Energy 23 (1998) 531544.
[16] S. John, J.C. Hamann, S.S. Muknahallipatna, S. Legowski, J.F. Ackerman, M.D.
Argyle, Energy efciency of hydrogen sulde decomposition in a pulsed corona
discharge reactor, Chem. Eng. Sci. 64 (2009) 48264834.
[17] M.V.V.S. Rao, S.K. Srivastava, Electron impact ionization and attachment cross
sections for H2S, J. Geophys. Res. 98 (E7) (1993) 1313713145.
[18] S.M. Avdeev, M.V. Erofeev, V.S. Skakun, E.A. Sosnin, A.I. Suslov, V.F. Tarasenko,
D.V. Schitz, Spectral and energy parameters of multiband barrier-discharge
KrBr excilamps, Quantum Electron 38 (2008) 702706.
[19] X. Feng, S. Zhu, Investigation of excimer ultraviolet sources from dielectric
barrier discharge in krypton and halogen mixture, Phys. Scr. 74 (2006) 322
325.
[20] U. Kogelschatz, Dielectric-barrier discharges: their history, discharge physics,
and industrial applications, Plasma Chem. Plasma P 23 (2003) 145.
[21] Y. Itikawa, Cross sections for electron collisions with nitrogen molecules, J.
Phys. Chem. Ref. Data 35 (2006) 3153.
[22] Y. Itikawa, Cross sections for electron collisions with oxygen molecules, J. Phys.
Chem. Ref. Data 38 (2009) 120.
[23] J.T. Herron, Evaluated chemical kinetics data for reactions of N(2D), N(2P), and
N2(A3 R
u ) in the gas phase, J. Phys. Chem. Ref. Data 28 (1999) 14531483.
[24] W.B. Demore, S.P. Sander, D.M. Golden, R.F. Hampson, M.J. Kurylo, C.J. Howard,
A.R. Ravishankara, C.E. Kolb, M.J. Molina, Chemical kinetics and photochemical
data for use in stratospheric modeling, JPL Publication 974, Jet Propulsion
Laboratory, California Institute of Technology, Pasadena, CA, 1997.
[25] R. Atkinson, D.L. Baulch, R.A. Cox, J.N. Crowley, R.F. Hampson, R.G. Hynes, M.E.
Jenkin, M.J. Rossi, J. Troe, Evaluated kinetic and photochemical data for
atmospheric chemistry: Volume I gas phase reactions of Ox, HOx, NOx and SOx
species, Atmos. Chem. Phys. 4 (2004) 14611738.
[26] S.D. Thompson, D.G. Carroll, F. Watson, M. ODonnell, S.P. McGlynn, Electronic
Spectra and Structure of Sulfur Compounds, J. Chem. Phys. 45 (1966) 1367
1378.
[27] G.N.A. Van Veen, K.A. Mohamed, T. Baller, A.E. Devries, Photofragmentation of
H2S in the rst continuum, Chem. Phys. 74 (1983) 261271.
[28] L.C. Lee, X. Wang, M. Suto, Quantitative photoabsorption and uorescence
spectroscopy of H2S and D2S at 49240 nm, J. Chem. Phys. 86 (1987) 4353
4361.
[29] B.R. Weiner, H.B. Levene, J.J. Valentini, A.P. Baronavski, Ultraviolet
photodissociation dynamics of H2S and D2S, J. Chem. Phys. 90 (1989) 1403
1414.
[30] S.H.S. Wilson, On the near ultraviolet photodissociation of hydrogen sulphide,
Mol. Phys. 88 (1996) 841858.
[31] Y. Itikawa, Cross sections for collisions of electrons and photons with oxygen
molecules, J. Phys. Chem. Ref. Data 18 (1989) 2342.