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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.
1067
Air blower
Exhaust
High voltage
power supply
Inner
electrode
Sampling/
Detection system
DBD reactor
Pressure
gauge
Outer
electrode
Kr + Br2
Volume flowmeters
1068
errors stated in the present work are statistical errors for a condence interval of 95%.
90
gH2 S %
80
70
60
50
40
30
20
10
Bare DBD
-10
H2 Sinlet H2 Soutlet
100%
H2 Sinlet
20
40
60
80
100
120
140
e Kr ! Kr 2e
e Br2 ! Br Br
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
1069
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].
Table 1
Energy utilization at Kr pressure.
Inner barrier lling gases
g (%)
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
14.0
38.1
56.8
97.3
111.6
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
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
1070
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
0
0
20
40
60
80
100
120
8
3.4. Applied voltage effect
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
g (%)
EY (mg kW h1)
EC (eV/mol)
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
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
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
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
1071
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)
100
ARA (g s1)
80
60
20
-1
0
3
H2 S e ! H HS
17
9
H2 S e ! H2 S
17
10
H2 S e ! 2H S
17
11
1072
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
13
O2 e ! O2
14
21
N2 A3 Ru H2 S ! N2 H HS 23
1
s1
15
H2 S O3 P ! OH HS 24
1
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
S O2 ! SO O 25
s1
19
SO O2 ! SO2 O 25
1
s1
20
s1
21
SO3 H2 O ! H2 SO4
reactor wall
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
H2 S hm ! H HS 29; 30
24
The subsequent oxidation of H and HS resembled those fragments originated from electron attack.
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.
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