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Chemical Engineering Journal 228 (2013) 1066–1073

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Chemical Engineering Journal
journal homepage: www.elsevier.com/locate/cej

Energy efficiency in hydrogen sulfide 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 efficiency were influenced 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 sulfide
Kr–Br2 excimer
Energy efficiency

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 filling gas pressure, applied voltage, and inlet H2S concentration were altered with the aim to improve the energy efficiency. High H2S removal efficiency could be
achieved with sufficient 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 efficient destruction of H2S by combined plasma photolysis process.
Ó 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 effluents, 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 Ó 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-filtration, 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-filtration, despite of low
cost, is easily influenced by many physical and chemical parameters
and in consequence unstable. Photocatalysis techniques demonstrate promising removal efficiency. 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
UV–VUV radiant power and long lifetime. However, most of these
light sources are still under laboratorial investigation and need further improvement especially in energy efficiency.

it consists of a continuous gas flow control and distribution system. Before sampling. and radicals are generated under high voltage electric fields in dielectric barrier discharge. gas was fed into the reactor at atmospheric pressure and ambient temperature (295 ± 2 K).) and air flow rate using mass flow controllers. and the flow rate was fixed at 0. we are able to provide some prospective on the future development of this technique. The simultaneous photolysis and plasma treatment were found to favor both pollutant removal efficiency and energy efficiency. To develop and advance this technique to industrial application. 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. The discharge is driven by a homemade square wave high-voltage supply capable of delivering voltage from 0 to 10 kV at fixed frequency of 20 kHz. the inner diameter of the outer barrier was increased to 40 mm as compared with our previous work. Huge amount of highly reactive species including energetic electrons.9%. In all experiments. Experimental setup The experimental system. was oriented vertically with gas flow from bottom to top. / Chemical Engineering Journal 228 (2013) 1066–1073 Studies have shown that dielectric barrier discharge (DBD) is especially capable of decomposing various pollutant gases [5. applied voltage. however. Since this is the first time we compare the performance of CDBD reactor with different halogen for the same pollutant removal. more laboratory studies are required either to extend the technique to other pollutant removal or to obtain the optimal operation conditions. In 2007. Nanjing Mucop Nanfen Special Gas Co. the mechanism for H2S decomposition under combined plasma photolysis treatment was proposed. The CDBD 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. 1. shown in Fig. meaning CDBD technique offers an alternative for H2S abatement. H2S removal efficiency and energy efficiency were carefully evaluated as a function of filling gas composition. Huang et al. a CDBD reactor. Both inner barrier and outer barrier are made of quartz.6]. 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 efficiencies have been achieved [7–9]. a power supply and gas sampling system. 1. The desired concentration of H2S–air gas mixture ranging from 0 to 150 mg m3 was generated by carefully adjusting H2S (99. In our previous work [11]. is similar to our previous work [11]. The inner barrier was made up of two co-axial quartz tubes sealed at the ends and filled with a mixture of Kr and Br2. Schematic diagram of the experimental setup for H2S removal. the whole setup was allowed to run for 20 min to make sure steady state had reached. . Both of the inner barrier and outer barrier are 200 mm in length.1. 2. a stainless steel band 4 mm in width. Here. The accurate power dissipated into the plasma was determined by a high voltage probe and a digital oscilloscope (Tektronix). The outer electrode. Removal efficiency higher than 90% could be reached at optimal test condition. It has an inner diameter of 10 mm and outer diameter of 20 mm. The energy efficiency.471 L s1 unless otherwise stated. Materials and methods 2. The inner electrode is a stainless sheet fitting tightly with the inner wall of the inner barrier. The averaged results are reported in the paper. was still less than satisfactory for industrial operation. In brief. this technique shows low energy efficiency and in turn constrains its industrial application. we further improve our combined plasma photolysis system with the purpose of enhancing the overall energy efficiency of the reactor. No systematic investigation on the influence of operation parameters on pollutant removal was given. we addressed the performance of H2S removal by dielectric barrier plasma and UV–VUV irradiation from a CDBD reactor using I2 as halogen. is wrapped around the outer side of the outer barrier. our group proposed to fill up the inner barrier with halogen along with rare gas so that VUV–UV irradiation would be spontaneously ignited when high voltage was applied [10].1067 L. cylindrical in shape. The premixed gas was then introduced into CDBD reactor by tunable air blower. Thus. This work only demonstrated a feasibility test on the idea of combined dielectric barrier discharge and photolysis (CDBD). Additionally. we performed three independent experiments. and inlet H2S concentration. In order to increase energy efficiency. Despite the high removal efficiency.5 cm3. atoms. the total volume of CDBD was enlarged to 188. For each experimental condition.

5% at inlet H2S concentration of 110 mg m3. KrBr excimer formed from Kr and Br2 mixture discharge had been frequently reported to generate intense narrow bandwidth ultraviolet irradiation. 222-nm and 228-nm irradiations are in good accordance with the characteristic emissions of KrBr excimer due to B1/2 ? X1/2. The emissions from CDBD device.3 Pa Kr and 133. The emission lines of 207. e þ Kr ! Krþ þ 2e ð2Þ e þ Br2 ! Br þ Br ð3Þ SED ðJ=LÞ ¼ P=ð1000  Q Þ Therefore. The significant increase of H2S removal efficiency in the presence of Kr and Br2 might be related to the absorption spectrum of H2S. Br2) in the inner barrier. Results and discussion 3.4% 228-nm irradiation.3 Pa Br2 in inner barrier. 3. H2S removal efficiency jumped from 16. The enhancement of H2S removal efficiency turned significant when H2S concentration was higher than 40 mg m3. the simultaneous irradiation due to Kr and Br2 mixture discharge. KrBr excimers are readily produced by a three-body ionic recombination reaction or harpooning reaction: ARA ðg=sÞ ¼ ½H2 Sinlet  gH2 S  Q  103 Kr þ Br þ M ! KrBr þ M ð4Þ Kr þ Br2 ! KrBr þ Br ð5Þ EY ðg=kW hÞ ¼ 3600  ½H2 Sinlet  gH2 S =SED  EC ðeV=moleculeÞ ¼ SED ð½H2 Sinlet  ½H2 Soutlet Þ  106  1:6  1019  N A =M H2 S where P is the power dissipated in the plasma (in W). excited molecule.2% 207-nm irradiation.0 ± 1.5 eV to 26. H2S molecule has a broad absorption band ranging from 160– 260 nm with peak centered at 195 nm. energy yield (EY.3 Pa Br2+ 1. represents the amount of energy deposited in per volume gas).5% was far lower than that obtained in this study by using 133. H2S concentration was then determined by the absorbance at 665 nm according to Lambert–Beer Law. and buffer gas. plasmas are created not only within the pollutant gas stream but also within the filling gases (e. while the energy required to remove single H2S molecule decreased from 106. followed by reacting with FeCl3 to form methylene blue.0 mg m3 using 47 kPa Kr and 2 mg I2 mixture as inner barrier filler (applied voltage was 7. in addition to direct discharge. 90 2. Since the inner diameter of the outer barrier was increased in this study.5 kV). H2S in the gas stream was absorbed by N.2. represents the quantity of target compound decomposed in unit second).3 Pa. 2.5 kV and flow rate was 0.33 kPa Kr ηH2S for 133. 2. . e þ Kr ! Kr þ e ð1Þ where e represents for high-energy electron and M represents anything that can serve as collisional third partner such as ion. contributed to the decomposition of H2S. In order to evaluate the importance of the type of filling compounds. atom. Huang et al. In our previous work. Improvement of removal efficiency and energy consumption by simultaneous non-thermal discharge and UV irradiation When high voltage is applied. The 207-nm. Analytical methods The concentration of H2S was quantitatively measured by colorimetric method which had been described in detail in our previous work [4]. Kr þ Br2 ! Kr þ Br2 ð6Þ Br2 ! Br þ Br þ UV radiation ð291 nmÞ ð7Þ With respect to the absorption cross sections of H2S [13]. With the addition of 133.1% 222-nm irradiation. As shown in Fig. the filling of 47 kPa Kr and 2 mg I2 mixture was also found to enhance the removal efficiency of H2S [11]. proving the generation of KrBr excimer during dielectric barrier discharge. C3/2 ? A3/2.3 kPa Kr 10 ηH2S for 133. applied voltage = 7.3 Pa Kr 20 ηH2S for 133.g. as recorded by a vacuumultraviolet spectrometer (American Acton Research Corporation VM-505) coupled to a photomultiplier tube with sodium salicylate fluorescent coating. Under the attack of high-energy electrons. MH2S is the molar weight of H2S (in g/mol). represents the energy necessary to remove one molecule). / Chemical Engineering Journal 228 (2013) 1066–1073 errors stated in the present work are statistical errors for a confidence interval of 95%. 2. Kr. [H2S]inlet and [H2S]outlet are the inlet and outlet concentrations of H2S (in mg m3). the UV irradiation from excimers.9% to 65. and therefore KrBr excimer based light sources were widely used [12].7 kPa Kr Bare DBD 0 ηH2S for 2mg I 2 + 47 kPa Kr -10 ½H2 Sinlet  ½H2 Soutlet  100% ½H2 Sinlet 0 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 specific energy density (SED. NA is the Avogadro constant (6. and 12.3 Pa Br2+ 133.N-dimethyl-p-phenylenediamine solution in acidic medium.3 Pa Br2+ 26. The removal efficiency of 40. Fig.3 Pa Kr and 133. H2S removal efficiency and energy consumption as a function of Kr pressure at various initial H2S concentration (PBr2 = 133.02  1023 molecule/mol for ideal gas).3 Pa Br2.1068 L.1. absolute removal amount (ARA. contributed to H2S removal in our device. 2). The energy efficiency was therefore significantly improved. Q is the gas flow rate (in m3 s1).5 eV. we could not compare current data with our previous results directly. consisted of 80.7 ± 27.3% 291-nm irradiation.3 Pa Br2 +13. in addition to direct electron attack. 5. The destruction and removal efficiency of H2S (gH2 S ) in CDBD reactor could be easily calculated from the following formula: gH2 S ð%Þ ¼ Removal efficiency (%) 80 70 60 50 40 30 ηH2S for 133. In brief. The small amount of 291-nm irradiation came from Br excimer relaxation to its ground state. we selectively tested H2S removal efficiency at initial concentration of 110. represents the quantity of odorous compound decomposed for a given energy) and energy cost per molecule (EC. Kr and Br2 are either excited or ionized [12].471 L s1) (see Fig. and B1/2 ? A1/2 transitions.

2 16.6 1437.2 ± 3.0 ± 4.6 ± 7.3 Pa Kr and 133.5% when inlet H2S concentration increased from 12.6 1160.4 133. Br2 pressure effect Shown in Fig.0 109. Apparently.0 ± 1.6 75. Despite the extensive study on H2S decomposition in non-thermal plasma in the past few decades.97 13.6 ± 2. Similar or better energy consumption was only reported by Cox et al. This is pretty exciting from the energy consumption point of view.8  1019 cm2 [17].1069 L.9 ± 4.5 74. There were no discernible differences in either removal efficiency or energy efficiency between these two Br2 pressures at the inlet H2S concentration range studied. the filling gases pressure and ratio have substantial influence on excimer emission intensity.01 ± 1.1 111.5 . However.8 29.9 502.87 8.31 19.5 ± 3.3 ± 4.73 ± 1.52 9.0 ± 7.5 ± 3.8 ± 3.3 ± 30. For a given applied voltage and gas flow rate.4 86.3 Pa Br2 + 1.8 97.1 ± 8.2 49.3 ± 85.0 eV with value of 1.5 ± 3.61 124.6 26.4 113.1 ± 4.3 eV/molecule [11]. the density and energy of primary charged particles. the averaged number of charged particles.2 108.10 52.3 Pa Kr 12. the energy consumption for low concentration H2S treatment in air at atmospheric pressure is far from acceptable for commercial application.3 ± 1.0 80.6 ± 2.5 30.31 ± 0.60 31. 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 1019–1018 cm2 mol1 [13]. 3.3 Pa Kr. and 228 nm originated from KrBr lie perfectly in this absorption band. The removal efficiency of H2S decreased from 86.0 34.4 126.4 45. energy consumption at optimal condition was still 74 ± 5.6 27.5 ± 10.5 78.7 ± 4.3.5 ± 81. and photons were constant.75 30. it is fairly reasonable that a better H2S removal efficiency and in consequence a better energy efficiency are achieved by addition of 133.4 154. Similar trends were obtained for inner barrier filled with 66.63 207.7 ± 11. electrons and photons that was able to attack each H2S molecule reduced.7 ± 9.2. Both active species (electrons.1 554. 2 also showed the evolution of H2S removal efficiency as a function of inlet H2S concentration.1 54.2 62.2 6.7 87.79 ± 0.2 335.3. It is noteworthy that H2S removal efficiency tends to be stable when inlet H2S concentration exceeds 80 mg m3 with Br2 as inner barrier filling gas.6 to 115.1 371.2 ± 53.2 106.7 kPa Kr 7.4 ± 1.2 70. 3 were H2S removal efficiencies obtained when the inner barrier was filled with 66.1 ± 8.3 ± 4.25 8. H2S removal efficiency only dropped slightly with increasing inlet H2S concentration when employing Br2 as filling gas.8 179.5 60.6 67.8 ± 65.6 ± 4.3 ± 5.07 8.39 25.50 ± 0. Although the ignition of KrBr excimer consumes some input power.3 ± 4. A gradual decrease of removal efficiency with inlet H2S concentration was observed.7 ± 3.1 52.7 106.9 115.5 ± 2.6 133.3 352.3 735. With the increase of inlet H2S concentration.9 59. radicals.7 ± 9.5 ± 3. further increase of Br2 pressure led to a drop in removal efficiency and a corresponding increase in energy cost. Influence of filling gases pressure In light of previous investigations on DBD driven excimer light sources [18].0 ± 1.09 ± 2.3 65.7 ± 4.6 ± 3.5 32.5 kV and 133.1 ± 4.28 ± 1.59 21.3 1174.9 300.45 ± 0.0 100. [16] at high H2S concentration.1 ± 39.4 ± 6. Table 1 summarizes the absolute removal amount (ARA).4 ± 4.72 ± 1.2 145.1 350. Even though our previous combined silent discharge and photolysis study to some extent improved the energy utilization in non-thermal plasma treatment.2 65.1 68.8 ± 23.48 35.86 28.4 35.2 83.1 ± 8. Taking into account the absorption cross section of H2S at 207 nm is four times larger than that at 183 nm [13]. The applied voltage was fixed at 7.9 31.9 ± 10.01 207.1 5.19 242.6 52. / Chemical Engineering Journal 228 (2013) 1066–1073 222.3.6% to 65.4 ± 3. the pressures of Br2 and Kr pressure inside inner barrier were varied.2 1055.76 ± 0.19 ± 0. Inlet H2S concentration effect Fig.3 kPa Kr ARA (g s1) EY (mg kW h1) EC (eV/mol) 5.3 Pa Br2 + 133.4 ± 34.2 ± 1.2 ± 1.2 ± 58.1 Bare DBD 3.0 716.2 ± 2.3 462.9 ± 31.8 105.1 ± 4. Typical energy consumption for low concentration H2S conversion in pulsed corona discharge reactors is over 100 eV/ 3.33 kPa Kr 14.5 48.2 ± 1.5 48. radicals and ions) attack and UV photodissociation induced H2S removal from gas stream in CDBD.7 424.68 ± 2.6 66.3 83. the cross sections for dissociative electron attachment for H2S peaked at 2. To check the potential influence of filling gas on H2S removal efficiency and energy efficiency.49 10.4 88.3 ± 64.7 ± 3.0 767. and energy cost (EC) information at each tested experimental condition. 266. Energy cost for each H2S molecule is as low as 26.3 ± 43.2 718.2 ± 1.7.4 ± 88.34 ± 0.87 18. radicals.2 80.3 ± 5.9 42.9 36.0 ± 2.13 7. [15] achieved at low pressure and John et al.8  1018 and 4.8 ± 5.6 ± 64.1 43.3 ± 59.05 8.6 ± 4.7 ± 1.77 17.5 ± 3.3 ± 3.70 ± 1.3 ± 19.6 22.8 94.27 12.2 50.1 296.9 73.1 ± 13.0 76.3 Pa Br2.3 Pa Br2 + 13.15 ± 0.6 ± 56.8 35.7 1218.4 mg m3 with inner barrier filled with 133.4 mg m3.3 111.8 ± 6.3 ± 35.22 ± 1.01 ± 0.7 Pa Br2 respectively. According to literature.08 ± 0.1 37.0 3. as presented in Table 2.1 56. 3.1 ± 35.2 67. A similar trend of Br2 pressure influence on DBD driven KrBr Table 1 Energy utilization at Kr pressure.7 and 666.1 1020.5 55.45 ± 0.1 69.3 Pa Br2 in inner barrier.6 859.6 ± 12.47 23.5 eV/molecule at inlet H2S concentration of 115.1.72 ± 1.7 and 133.3 Pa Kr was served as rare gas in inner barrier. energy yield (EY). 133. Inner barrier filling gases Concentration (mg m3) g (%) 133.44 26. Huang et al. EC drops dramatically with increasing inlet H2S concentration.2 60.5 ± 21.5 15.28 11.3 41.7 ± 27.2 39.29 ± 0.7 ± 70. electrons.14 ± 0.4 ± 7.2 and 9.3 Pa Br2 and 133.0 38.3 66.2 180. Unlike using I2 as inner barrier filling gas. molecule [14].7 133.8 1279.3 Pa Br2 + 26.99 29.1 353.8 ± 2.1 1.7 ± 80.6 ± 5.5 ± 3.

2 ± 27.4.1 919.3 65.2. The discrepancies in removal efficiency were especially significant at inlet H2S concentration higher than 45 mg m3. (2).7 Pa Br2 ηH2S for 133. while more KrBr were quenched by krypton atoms to form triatomic species at high pressure.02 1.1 ± 3.4 ± 4.4 799. However.9 78.5 ± 81.22 30.7 62.2 1055. It is an important component for the generation of KrBr according to Eqs.0 ± 1.8 64.3 ± 1.4 35.9 4.7 Pa Br2 + 133.6 971.3 ± 24.4 ± 3.6 ± 6.0 ± 48.5 74. It demonstrated a decay trend with the further increase of Kr pressure. 42.5 kV.3 90. 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 [18.68 16. H2S removal efficiency peaked at Kr pressure of 133.4 97.5 kV.5 ± 1. H2S removal efficiencies obtained with the addition of 133.1 ± 12. 1330.0 ± 72.7 Pa Br2 + 133.38 ± 1. 13300.6 65.3 Pa Br2 20 ηH2S for 133.9 396.5 ± 2.1 110.5 ± 1.8 ± 63.5 116.9 55.5 ± 10.9 ± 57.1 80. we may easily find out only the emissions due to KrBr excimer contribute to the photodissociation of H2S.7 57. and 35. In this study.4 706. Different from our previous work [10]. 65.8 107.3 Pa Kr 10.20 19.1 1289.57 24.3 Pa Kr 5.3%.3 Pa Kr 1.9 102.6 1437.3 Pa Kr + 133. [18].5 ± 3. Applied voltage is another predominant factor that may influence H2S removal efficiency due to its potential influence on energy dissipation in the reactor. H2S removal efficiency and energy consumption at various Br2 pressure when applied voltage was 7.2 36.8 ± 3.2 ± 4.07 ± 0. and 26700 Pa Kr.7 5.9 45.1 353.59 21.23 ± 2. H2S removal efficiencies were 16.27 29.6 67.1 ± 8. Inner barrier filling gases Concentration (mg m3) g (%) EY (mg kW h1) EC (eV/mol) 66.39 13.9 ± 25.0 80.9 33. 3.3 Pa Kr were the highest among all Kr pressures tested.21 ± 1.3 89. Br2 plays a crucial role in the formation of KrBr excimer.62 3.47 18.0 ± 2. Comparing the emission of Kr–Br2 mixture under discharge and the absorption spectrum of H2S.9 ± 2. The number of KrBr excimer increased as a result of increasing ionic krypton at low Kr partial pressure.3 ± 4.0 31.7 ± 86.7 ± 89.3 ± 5.3 Pa Kr + 66.9 mg m3 respectively.44 26.4 52.3 Pa Kr + 666.9 1103.24 9.3.3 39. It was because H2S removal efficiency was the only factor that had impact on energy cost at given applied voltage. (1).8 76.3 and 41.3 ± 59. (4). / Chemical Engineering Journal 228 (2013) 1066–1073 7.3 Pa Kr + 266.25 8.4 ± 2.06 17.33 Pa and applied voltage of Table 2 Energy utilization at Br2 pressure.2 180. gas flow rate.2 ± 58.2 ± 4.7 Pa Br2 0 0 20 40 60 80 100 120 [H2S] (mg m-3) Fig.3 ± 1.0 2.1 ± 70.9%.1 ± 0.33 ± 0.0 96.1 45.7 38. As shown in Fig.2 ± 1.9 115. As a rare gas.1 ± 51.6 ± 4.7 ± 3.6 133.5% respectively at inlet H2S concentration around 115.5%.6 Pa.81 ± 1. H2S removal efficiency 3.8 ± 23.3.4 654.6 859.9 64. however. Removal efficiency (%) 100 80 60 40 ηH2S for 133.7 ± 55.0 46.6 ± 2.7 ± 5. Fig.8 1223.5 30.9 618.6 1018.3 55.4 ± 1. Kr pressure effect The influence of Kr pressure on H2S removal by CDBD was then investigated at Br2 pressure of 133.9 96.30 41.0 mg m3 with addition of 0. Applied voltage effect  The total radiation power of KrBr began to decrease with Br2 pressure after achieving a maximum value.7 1218.1 63.5 66.0 ± 9.1 ± 4.7 563.14 ± 0.6 ± 4.76 ± 0.74 22.6 22.0 60.5 ± 3.3 54.41 31.6 ± 5. A possible explanation for this phenomenon was that the increase of filling 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.08 6.7 ± 1. Kr pressure would impact the emission intensities from Kr–Br2 mixture driven by DBD in multiple ways.8 94.1070 L.4 ± 5.6 ± 4. (3)–(5).6 799. 60.9 ± 3. KrBr þ Br2 ðBrÞ ! Kr þ Br þ Br2 ðBrÞ ð8Þ 3.8 ± 1.19].3 ± 5.14 169.3 Pa Br2 + 133.8 88.9 ± 2.1 ± 15.7 ± 3.05 19.6 666.6 221.7 82.7 49. and inlet H2S concentration. 4 presents the variation of H2S removal efficiency with applied voltage at inlet H2S concentration of 3.8 105.2 60.80 27.4 ARA (g s1) 0.1 76.6 26.5 ± 3.3 99.3 1192.91 ± 0.2 279.2 83. no adverse effect was observed over all the reaction conditions tested as compared with bare DBD treatment.78 ± 2.5%.6 75.9 366. 2.3 52.1 43.1 68.5 ± 5.3 ± 4.34 25.3 823. excimer lamp in terms of emission power was reported by Avdeev et al.3 Pa and total filling gas pressure of 266.1 . 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.7 ± 70. The influence of filling gas pressure on energy efficiency (see Table 3) was in analogy with its influence on H2S removal efficiency.9 ± 3. Total radiation power of KrBr initially increased with Br2 pressure.76 ± 0.9 ± 42.9 40.37 20. Huang et al.05 ± 1.50 ± 0.4 86.5 266.33 ± 2. As indicated in Eqs.48 35.1 ± 7.2 ± 4.97 ± 1.7 46.8 25.7 Pa Br2 + 133.7 ± 4.01 207.3 ± 3.5 ± 1.8 ± 5.7 Pa Br2 ηH2S for 133.3 Pa Kr 12.2 57.8 ± 3.9 ± 7.75 30.7 ± 94.2 ± 1.1 ± 5.4 ± 83.08 94.19 ± 0.5 ± 2.9 ± 13. 133.0 133.6 ± 7.5 29.

As a result.8 81. Direct electron attack According to Rao’s study [17].3 ± 20. The variation of energy yield and energy cost with applied voltage turned out to be far more complicated.2 89.due to direct electron attack was extremely high.7 142.9 109.6 874. electric field in the discharge gap high enough to cause break down was required. 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. indicating extensive decomposition reaction of H2S took place. leading to a low energy yield and energy cost. evidenced by vacuum-ultraviolet spectroscopy.5 kV. Byproducts analysis and decomposition mechanism 40 20 -1 ηH2S at [H2S]0 = 41.8 ± 7. As illustrated in Table 3.9 109.9 mg m3 respectively (PKr = 133.05 1.3 ± 3.2 ± 5. the probability for H2S dissociation into HS.9 ± 3.52 7.8 6.26 ± 0.8  1018 cm2. in which active discharge species and energy dissipation mainly accumulated. The gases after CDBD treatment (applied voltage was 7. Provided that gas flow rate was fixed. ARA was a function of removal efficiency. a large amount of microdischarges were formed within the space between electrodes. / Chemical Engineering Journal 228 (2013) 1066–1073 Table 3 Energy utilization at different applied voltage.6 74.9 mg L -1 ηH2S at [H2S]0 = 3. H2 S þ e ! H2 þ S ½17 ð10Þ H2 S þ e ! 2H þ S ½17 ð11Þ 3.1 ± 1.1 60.0 kV region.8 ± 81. the mechanisms for pollutant decomposition are still under debate.7 ± 33. In the meanwhile. 80.9 3.7 ± 2.69 11. H2 S þ e ! H þ HS ½17 ð9Þ  The appearance of a small amount of S was also expected as a result of the direct electron attack of H2S.4 ± 0.6 650.06 1.3 706.6 ± 21. The increase of applied voltage brought about an enhancement in the density of microcharges. indicated by EY and EC.9 500.7 231.6 ± 6.3 41.2 99.4 88.61 10.0 ± 2.5 kV) were harvested by a liquid nitrogen trap at the downstream of reactor.7 ± 6. 4.3 ± 3.3 Pa.3 Pa).67 9.8 mg m3 H2S was continuously introduced into reactor at flow rate of 0.7 919.demonstrated a peak at 2.5.2. absolute H2S removal amount exhibited similar trend as H2S removal efficiency with applied voltage. there were three predominant mechanisms responsible for H2S decomposition.54 ± 0. However. inlet H2S concentration and gas flow rate.6 189.4 ± 4.90 ± 0.3 3. increased monotonously with applied voltage.0 ± 5. their direct collisions with electrons were inevitable. the input energy also increased significantly.6 ± 5.3 ± 4.8 ± 18.1 ± 1.5 ± 93. most energy was consumed in the excitation of plasma instead of the removal of target pollutant.5–6. 3. dropped after the applied voltage exceeded 7. ARA was only influenced by H2S removal efficiency at given inlet H2S concentration.5 52.0 51. At low inlet H2S concentration.50 ± 0.1071 L.4 ± 1. Moreover.5 kV.1 ± 3.1 ± 4. The only discernible product in gas stream exiting CDBD reactor was H2O. Huang et al. To initiate discharge.7 ± 4. H2S removal efficiency as a function of applied voltage at initial H2S concentration of 3.6 189.9 ± 4.4 ± 2.5 ± 20.2 ± 57.5 9. Typical voltage needed to establish plasma in barrier dielectric reactor operating under atmospheric pressure was around several kV [20].7 142.0 ± 2.5.3 51.0 35.7 88.0 7.4 74. Once breakdown occurred.1.0 ± 5. H2S removal efficiency increased with the applied voltage accordingly.7 231.5.8 4. the concentration of S would not accumulate to significant level. the cross sections for dissociative electron attachment for H2S to form HS.8 6.0 ± 48.1 ± 1.7 57.6 4.5 ± 16.6 4.3 and 41. Based on previous literature reports and experimental results. Therefore. 100 Removal efficiency (%) ARA (g s1) 80 60 3.6 422.0 40.6 730. Since the cross sections for dissociative electron attachment for H2S to form S were far smaller than those to form HS [17]. the trapped gases were warmed to room temperature and then subjected to FT-IR analysis. Concentration (mg m3) Voltage (kV) g (%) SED (J L1) 3. the energy efficiency of CDBD reactor.04 ± 0.31 ± 0. the UV emission intensity from the CDBD reactor increased with applied voltage either.8 618. Considering most electrons in dielectric barrier discharge possessed energy in the range of 0–10 eV.6 63. The success of byproducts analysis might contribute to a better understanding of removal mechanism under CDBD.6 74.2 eV with value of 1.4 EY (mg kW h1) EC (eV/mol) of collision between active species (electrons.7 ± 3.07 1.06 ± 0.28 402.8 42.471 L s1.7 96. could be regarded as a miniature plasma chemical reactor.3 mg L 0 3 4 5 6 7 8 9 Applied Voltage (kV) Fig.04 92. The variation of energy efficiency of CDBD exhibited the combined effect of applied voltage on active species generation and total energy input.3 ± 4.5 9.83 ± 0.6 ± 4. After 30-min collection.18 ± 0. With . Each individual microdischarge.1 ± 3.28 724.39 ± 0.07 1. It is therefore necessary to perform byproducts analysis to address the safety of current technique. The increase was more apparent when applied voltage altered in the 4.1 99.0 7.0 57. In current research. Reactions with electron-induced excited species and free radicals Taking into account the partial pressures of N2 and O2 in gas stream.9 86. PBr2 = 133.6 ± 0. ions and photons) and H2S molecule.8 0. considerable H2S removal was observed when applied voltage exceeded 4.

Regarding the experimental results. N2 þ e ! N2 ðA3 Rþu Þ þ e ð½21Þ ð12Þ O2 ðX 3 Rg Þ þ e ! O2 ð2 Pu Þ ! O ð2 PÞ þ Oð3 PÞ ð½22Þ ð13Þ O2 þ e ! O2 ð14Þ ð½21Þ These electronic excited species and radicals contributed to H2S dissociation through either direct reactions with H2S or reactions with fragments from H2S decomposition. the amount of S in the form of S(VI)(45. Attractive performance has been achieved at optimal operation condition.5 eV/molecule was approaching the lowest energy cost ever reported for plasma reactor operated at non-vacuum pressures and diluted condition. Regarding the fast combination of H and OH radicals.3 Pa Kr. were capable of destroying most chemical pollutants. More laboratory-scale and pilot-scale studies dealing with different group pollutants are in demand of with the purpose to improve . 30Þ ð24Þ The subsequent oxidation of H and HS resembled those fragments originated from electron attack. led to the decomposition of pollutants. / Chemical Engineering Journal 228 (2013) 1066–1073 respect to the electron energy distribution in dielectric barrier discharge. 207-nm and 183nm photons.79 eV respectively. It is very likely that reaction occurred between SO3 and H2O. a decline in direct photolysis of H2S could be expected. According to IC analysis. a combined consideration of electric and optical properties should be taken into account when designing the optimal CDBD setup. is also worthy a shot. This might be caused by the further reaction of SO3.1072 L. 4. plasma-triggered excimer photodissociation. Prospectives of CDBD technique By far. most radiation would directly interact with H2S molecule when H2S was subjected to DBD combined Kr–Br2 photolysis treatment. indicating the high oxidation ability of CDBD technique. The target pollutant we selected was odorous inorganic compound H2S. H2S removal efficiency by DBD combined Kr–I2 photolysis was far lower than that by DBD combined Kr–Br2 photolysis. On the contrary. N2 ðA3 Rþu Þ þ H2 S ! N2 þ H þ HS ð½23Þ 1 k ¼ 3:0  1010 cm3 molecule s1 ð15Þ H2 S þ Oð3 PÞ ! OH þ HS ð½24Þ 1 k ¼ 2:2  1014 cm3 molecule s1 ð16Þ 1 s1 ð17Þ 1 s1 ð18Þ HS þ Oð3 PÞ ! OH þ S ð½24Þ k ¼ 1:6  1010 cm3 molecule HS þ O2 ! OH þ SO ð½24Þ k < 4:0  1019 cm3 molecule 1 k ¼ 2:1  1012 cm3 molecule S þ O2 ! SO þ O ð½25Þ s1 ð19Þ SO þ O2 ! SO2 þ O ð½25Þ 1 k ¼ 7:6  1017 cm3 molecule s1 ð20Þ SO2 þ Oð3 PÞ þ M ! SO3 þ M ð½24Þ 2 k ¼ ð1:3  0:7Þ  1031 cm3 molecule s1 ð21Þ However. It is time to reflect on the advantages and limitations of CDBD technique which may benefit its further improvement and the eventual industrial practice. It is noteworthy that the overall performance of CDBD technique may vary with different target pollutants because the removal efficiency is highly dependent on the dissociative electron collision cross sections and absorption cross sections of pollutants. 100 mL deionized water was used to rinse the wall of CDBD reactor. such as Kr–F2 and Kr–Cl2. SO3 þ H2 O ! H2 SO4 reactor wall H2 SO4 ƒƒƒƒƒƒ! surface adsorbed H2 O.3 Pa Br2 and 133. The foggy H2SO4 formed along with H2O vapor would later deposit on the wall of the reactor.3. H2 S þ hm ! H þ HS ð½29. With part of radiation absorbed by O2. indicating the pressure of filling gas may affect the energy dissipation between inner barrier filling gas and pollutant gas stream as well. The influence of inner barrier filling gas pressure on the performance of CDBD was systematically investigated in this work as well. The variations of H2S removal efficiency with filling gas pressure were not only controlled by the influence of filling gas pressures on KrBr excimer intensity. SO2 4 ð22Þ ð23Þ S(VI) was the only detectable sulfur-containing species in gaseous and liquid products. along with direct electron attack and electron-induced excited species and free radicals reaction. The optimal H2S removal efficiency and energy efficiency were achieved when inner barrier was filled with 133. The absorption cross sections of H2S in UV region have been studied by many research groups [13. The characteristic emissions of KrBr can readily cause H–S cleavage when absorbed by H2S molecule. Compared with that at 183 nm. the major processes could be expressed as following equations. while 183-nm light dominated the emission from Kr–I2 mixture. with energy of 6. In order to prove the assumption. 3. meaning most decomposed S would finally convert to S(VI). no sulfur-containing gaseous products were detected. as a major component in the gas stream. a different combination of rare gases and halogens. For each pollutant. Dielectric barrier discharge combined with Kr–Br2 photolysis showed predominant advantage over DBD combined Kr–I2 photolysis for H2S abatement both in removal efficiency and energy efficiency. competitively absorb radiations from excimer with cross section on the order of magnitude of 1020 cm2 mol1 at 183 nm [31]. Thus. H2 SO4 . our group has investigated the removal efficiency and energy efficiency 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.5. Energy cost for each H2S of 26 ± 1. the presence of H2O in the reactor was unavoidable. Dissociation by plasma-triggered KrBr radiation The significant promotion of H2S removal efficiency in the presence of rare gas and halogen in inner barrier and filling gas pressure dependent H2S removal efficiency had provided solid proofs that plasma-triggered KrBr radiation contributed to H2S dissociation as well. 207-nm light was identified as the dominant emission for Kr–Br2 mixture. One explanation was that the absorption cross section at 183 nm was lower than that at 207 nm. If necessary. It was well accepted that H2S had a broad absorption in the 160–260 nm region with a peak at 195 nm.26–28]. the absorption cross section of O2 at 207 nm was four orders of magnitude lower. The higher photon energy of 183-nm photon did not presumably bring about higher removal efficiency.01 and 6. as indicated by FT-IR. The other non-negligible reason was that O2. Huang et al.6 mg) in rinse water accounts for 97% of the total decomposed S from H2S.

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