Hindawi Publishing Corporation

Journal of Chemistry
Volume 2015, Article ID 414237, 9 pages
http://dx.doi.org/10.1155/2015/414237

Research Article
Removal of Ethanethiol Gas by Iron Oxide
Porous Ceramsite Biotrickling Filter

Peipei Wang,1,2 Shuchuan Peng,1,2 Chengzhu Zhu,1,2 Xiongjun Zhang,2 and Fei Teng1
1
Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, School of Environmental Science and
Engineering, Nanjing University of Information Science and Technology, Nanjing 210044, China
2
School of Resources & Environmental Engineering, Hefei University of Technology, Hefei 230009, China

Correspondence should be addressed to Shuchuan Peng; [email protected] and Fei Teng; [email protected]

Received 22 September 2014; Accepted 16 December 2014

Academic Editor: Jian Lu

Copyright © 2015 Peipei Wang et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

The performance of ethanethiol removal in biotrickling filter was investigated by microorganisms fixed on iron oxide-based porous
ceramsite (IPC) under different operating parameters conditions. Ethanethiol removal efficiency was examined as a function of inlet
concentration, empty bed residence time (EBRT), and spray density of nutrient solution. The results showed that the optimized
operation conditions and operation characteristics of biotrickling filter for this study were at the inlet concentration of less than
250 mg⋅m−3 , the spray density of 0.24 m3 ⋅m−2 h−1 , and the EBRT of 68.7 s. The variation of the EBRT of about 100 s and the spray
density of about 0.24 m3 ⋅m−2 h−1 did not change the ethanethiol removal efficiencies at certain ethanethiol concentrations of less
than about 300 mg/m3 , respectively. The main metabolic product was sulfate such as SO4 2− under continuous long-running regime
in filter. The ethanethiol desulfurization process better meets the Michaelis-Menien model with calculated kinetic degradation
parameters 𝐾𝑠 = 7.96 mg⋅m−3 and 𝑉𝑚 = 221.73 g⋅m−3 h−1 .

1. Introduction generally much more expensive [4]. However, the biological

technologies have been reported by some research to be a
Ethanethiol (ET, CH3 -CH2 -SH) is volatile organic sulfur promising effective alternative for desulfurization processes
compounds (VOSCs) with an intensive garlic odour; it for removal of VOSCs with low operating costs, low operating
is often used as malodorant and warning agent and is a requirements, and no by-products produced for disposal
significant organophosphorus pesticide intermediate [1, 2]. treatment moreover, they can process simultaneously two
ET is usually released from various industries and can cause or more contaminants [13–16]. Biotrickling filter and biofil-
different kinds of environmental problems. And when it tration processes are two sorts of biological desulfurization
functioned in the central nervous system of human body, process that have been widely applied [12, 14–18]. And
it could cause poisoning, headache, and nausea and even compared with other biological methods, biotrickling filter
lead to death due to respiratory paralysis [3]. Therefore, process was proved to have an advantage of higher rates of
it is desirable and catches many people’s growing concern mineralization [12, 19].
to develop new technologies or improve existing treatment In recent years, the biological treatment study of VOCs
technologies to control such VOSCs like ET nowadays. Lots such as ethanethiol could be mainly summarized about these
of physical and chemical abatement technologies, such as respects, the research for advantage microbial strains cultiva-
combustion method [4–6], oxidation process [7–9], and tion and living conditions optimization, the designation and
absorption method [10, 11], have been invented for purifying optimization of the biological reactor, as well as the biological
VOSCs. But their performance is not satisfying and they do filter, and the research for biodegradation dynamics. For
not really degrade VOCs. By some traditional physical tech- example, An et al. [12, 19] had inoculated with Lysinibacillus
nologies, VOCs may just be transferred from gaseous phase sphaericus strain RG-1 or RG-1 and B350 mixed microor-
to other phase [12]. Moreover, the chemical technologies are ganisms in biotrickling filter columns to remove ethanethiol
2 Journal of Chemistry

and single, binary, and ternary mixture gas of ethanethiol,

dimethyl disulfide, and thioanisole. However, both researches 2 4
had got satisfying results. And with the continuous devel-
1 13
opment of anaerobic technology [20–22], Arellano-Garcı́a
et al. [23] had used an aerobic biotrickling filter system T 3 5
for removal of waste gas containing ethanethiol from their C
published paper. In addition, Sedighi and Vahabzadeh [24]
8
studied the kinetic modeling of cometabolic degradation of 6
ethanethiol. Hernández et al. [25] had used biotrickling filters B
packed with poplar wood and polyurethane foam to remove
simultaneously H2 S, NH3 , and ET and investigate the impact 7
of pH during startup and crossed effects evaluation.
A
In present study, biotrickling filter system was employed S
in this study for the purpose of removal of target gas, 11
ethanethiol. Organic sulfide was absorbed by microorganism
fixed on packing materials (usually Thiobacillus such as T.
denitrificans, T. thioparus, and others) and then degraded and 9
10 12
transformed to inorganic sulfate or elemental sulfur [26–30].
The effects of the filter performance with different operating Figure 1: Biotrickling filter set-up and technological process (1:
parameters such as inlet concentration spray amount and liquid-flow meter; 2: sprinklers; 3: absorption bottle; 4: air pump;
empty bed residence time (EBRT) in the stage of start-up 5: ethanethiol reservoir; 6: peristaltic pump; 7: mixing gas tank; 8:
and stable-running were systematic investigated. In addition, compressor; 9: nutrient recirculation tank; 10: biotrickling filter; 11
dynamic analysis for this biological desulfurization process and 13: gas-flow meter; 12: buffered gas-bottle; S, A, B, C, T: sampling
was also preliminarily discussed. All of the research contents port).
would provide an effective technical reference for further
study and application about biotrickling filter.
the bottom of the filter, through three IPC filler layers, and
then outflew from the top. However, circulating nutrient
2. Materials and Methods solution was totally opposite, sprayed from the top to the
bottom lifted to reservoir tank by water pump (BQ5Q1-1J
2.1. Experimental Set-Up and Technological Process. Using
peristaltic pump, Baoding Longer Pump). And in order to
multilayer filler could improve the treatment efficiency and
sample output gas there was a sampling port in each layer.
stability of filtration column because of the decreased relative
Certain concentration of ET was prepared by the method
thickness of each layer which would reduce the weight of filler of dynamic preparation method. In other words, a small
of each layer and lead the filler difficultly to compact. While amount of air was bubbled into liquid ET solution in the
air flow was redistribute through each layer, so that the gas ethanethiol reservoir to produce the pure ET gas, then the
flow distribution could be more uniform, the flow rate could ET gas entered into mixing gas tank and mixed with air
decrease and the residence time could be longer. Huaxin et al. in order to form a certain concentration gas. Considered
[31] used natural corncob and sawdust as filter and divided environmentally, the exhaust gas compound flew through the
the column into three layers to remove H2 S; the results biotrickling filter was finally absorbed with 32% NaOH.
showed that, in the test inlet concentration, a multilayer
filter had a slight advantage over a single layer filter for the 2.2. Analytical Methods. The concentrations of ET were
removal of H2 S. However, the stabilization and the removal analyzed by the amino dimethyl aniline spectrophotometry
efficiency of biofilters were also improved. Chen et al. [32] (GBZ/T160.49-2004) [34]. And the performance of studied
used three pilot-scale immobilized-cell biotrickling filters for biotrickling filter was generally evaluated by
removal of hydrogen sulfide from a contaminated air steam
and got a good performance. In present study, the biotrickling 𝐶in − 𝐶ot
RE (%) = × 100, (1)
filter was a self-made plexiglass column (Figure 1) divided 𝐶in
into three layers with filter inner diameter of 90 mm and
the total reactor height of 1200 mm. Each layer was packed where 𝐶in (mg⋅L−1 ) is the inlet concentrations and 𝐶ot
with 200 mm height iron oxide-based porous ceramsite (IPC) (mg⋅L−1 ) is the outlet concentrations of gas compounds.
with particle size determined of about 5–8 mm. And the However, the various inlet loads 𝑁V (g⋅m−3 h−1 ) calculated
mud content was about 0.27%, hydrochloric acid soluble by (2) are also a significant parameter evaluating the filter
rate was approximately 0.43%, porosity was 71.48%, surface performance:
area was 7.1 × 105 cm2 ⋅g−1 , a bulk density was 0.46 g⋅mL−1 , 𝐶in ⋅ 𝑄
an apparent density was 1.71 g⋅cm−3 , ceramic strength was 𝑁V = , (2)
1000𝑉
about 51–78 N, and porosity ratio was about 40.5–64.3%. The
biotrickling filter was employed with up-flow running mode, where 𝑄 (m3 ⋅h−1 ) is gas volume flow of gas compounds of
a countercurrent operation [33]. Ethanethiol gas entered from ET and 𝑉 (m3 ) is the volume of studied biotrickling filter.
Journal of Chemistry 3

In addition, empty bed residence time EBRT (s) and spray 700 70
density 𝜌 (m3 ⋅m−2 h−1 ) as two necessary parameters can
600
calculated by

ET concentration (mg/m3 )
60
𝑉 500
𝑇= ⋅ 3600, (3)
𝑄
400

RE (%)
4𝑄𝑙 50
𝜌= , (4) 300
𝜋𝐷2
where 𝑇 (s) is EBRT and 𝑄 and 𝑉 in (3) are same as defined 200
40
above in (2); 𝑄𝑙 (m3 ⋅h−1 ) and 𝐷 (m) in (4) are liquid spray
flow and inner diameter of filter, respectively. 100
The energy of microbial growth metabolism provided 30
0
by only ethanethiol in the process of the biodegradation of 0 4 8 12 16 20 24 28
ethanethiol occurred in studied filter [30]. Because of the Running time (d)
biodegradation by microorganism, organic sulfate (ET) could Inlet
be transformed to inorganic sulfate or elemental sulfur such Outlet
as SO4 2− , which led the nutrient solution change sponta- RE
neously into acidification. If ET can be completely degraded,
the reaction is as follows [12]: Figure 2: The ethanethiol inlet and outlet concentration and
removal efficiency in start-up period.
C2 H5 SH + 5O2 󳨀→ 2CO2 + 2H2 O + H2 SO4 (5)
2−
In that case the concentration of SO4 was determined
through spectrophotometric method (GB/T13025.8-91) [35]. 3.2. Effect of Inlet Concentration on RE. In any biofiltration
The microbiological quality fixed on inorganic packing sur- desulfurization process the initial concentration was a sig-
face was observed by using Scanning Electron Microscope nificant parameter on RE [27]. To study the effect of inlet
(SEM, XL30 ESEM-TMP). concentration ranging from 100 to 500 mg⋅m−3 on RE in filter,
experiment operation condition was controlled at a temper-
3. Results and Discussions ature of about 20–25∘ C, spray density of 0.24 m3 ⋅m−2 h−1 ,
and EBRT of 60 s. The results were shown in Figure 4. It
3.1. Biotrickling Filter Start-Up and Running Performance. can be seen that the RE of ET was reduced when the inlet
Biotrickling filter started and run at certain conditions in concentration increased. 63.98% RE obtained decreased into
which the experimental temperature was 20∘ C–25∘ C, the 57.39% when the inlet concentration increased from 95.74
inlet concentration of ET was about 47.15–434.28 mg⋅m−3 , the to 501.39 mg⋅m−3 . While the inlet concentrations were less
spray density was about 0.08–0.31 m3 ⋅m−2 h−1 , and EBRT was than 250 mg⋅m−3 , the removal efficiencies of ET were about
60 s after inoculating tame activated sludge (Zhu Zhuanjing 64% and the magnitude of decreasing of RE was smaller. In
sewage treatment plants of Hefei, Oxidation ditch). The the study the maximum inlet load of the biotrickling filter
performance of biological removal of ET was presented in was 34.22 g⋅m−3 h−1 and the actual maximum oxygen con-
Figure 2 after 26 d. sumption was 88.30 g under the current biosystem according
Figure 2 showed that the ET removal efficiencies were to the stoichiometric degradation reaction. However, the
48.10%, 55.65%, and 61.45% on the 1st d, 4th d, and experiment condition of air in the biotrickling filter can
12th d, respectively, with concentration of ET less than provide more than 150 g oxygen. Thus, oxygen is sufficient
251.24 mg⋅m−3 . The removal efficiency stabilized at around for the microorganism to degrade ET in this biosystem. And
60% after a 18 days’ steady running of biotrickling filter with a higher concentration gradient of ET could be produced by
increased ET inlet concentration. However, 58.9% removal increasing inlet concentration, which would improve gaseous
efficiency was detected on 26th d. The biofilm biomass was biofilm mass transfer rate from liquid phase to gas phase [12].
also determined about 0.034 g⋅g−1 . And a white membranous But the reason of decreased RE of ET in this study probably
substance attached to packing materials was observed in filter could be summarized as reaction substances constraints or
by naked eye. It was also found that larger ellipsoid bacteria diffusion limitation regime [26]. In addition, as the initial
with dimensions of about 18 × 38 𝜇m with scaly structure are ethanethiol concentration increases, more time is needed to
present in packing materials surface. From the SEM results achieve the same RE because the lag phase of bacteria may be
(Figures 3(a) and 3(b)), the scaly structure had a serrated extended at higher concentrations of substrate [36]. However,
opening at one end. In addition, the substances immobilized biomass accumulation may be enhanced due to increase
on the surface of IPC filler were scraped to be observed under the gaseous compounds of ET inlet concentration with the
the microscope; the photo is shown in Figures 3(c) and 3(d). various inlet loads 𝑁V changed from 3.76 to 19.72 g⋅m−3 h−1 in
The freedom movement of rod-shaped microorganism could the process, so that the thickness of the biofilm could increase
be found obviously in the observation. In a word, biotrickling synchronously. As a result, the gas flow was obstructed
filter start-up of inoculated operation completed basically because the porosity of packing materials reduced which led
after 26 d. to decrease of biological activity [15].
 4 Journal of Chemistry

(a) (b)

(c) (d)

Figure 3: SEM images (a, b) and microscope photo (c, d) of IPC ceramsite after microbial inoculation.

400 65 70
Outlet concentration (mg·m−3 )

300 60
65
RE (%)

200 55
RE (%)

60
100 50

0 45
100 200 300 400 500 55
Inlet concentration (mg·m−3 ) 20 40 60 80 100 120 140
EBRT (s)
Outlet
(a) 200 mg·m−3
RE
(b) 300 mg·m−3
Figure 4: The effects of inlet concentration on ethanethiol removal (c) 400 mg·m−3
efficiency.
Figure 5: The effects of EBRT on ethanethiol removal efficiency.

3.3. Effect of EBRT on RE. EBRT was also a significant through increasing EBRT of biotrickling filter. Compared to
parameter of any biofiltration desulfurization process [12] three different inlet concentrations of effect of EBRT on RE,
and the effect of EBRT was studied at experimental condition it could be seen a higher RE value when the ET inlet con-
where temperature was about 20–25∘ C and spray density was centration was 200 mg⋅m−3 or 300 mg⋅m−3 than 400 mg⋅m−3 ,
0.24 m3 ⋅m−2 h−1 in biotrickling filter (Figure 5). The results and the RE value of group (a) and (b) was of similar at
indicated that the removal performance could improve lower EBRT. When EBRT increased to about 70 s an obviously
Journal of Chemistry 5

increased trend of RE was achieved with comparison value 70

of three group, 200 mg⋅m−3 > 300 mg⋅m−3 > 400 mg⋅m−3 .
In addition, better performance of RE was found at low
concentration than high concentration of ET. 65
As 3.2 described, ET biological degradation reaction
was mainly controlled by reaction substances constraints or

RE (%)
diffusion limitation regime. The reason for higher RE values 60
in longer EBRT condition was that the increased EBRT in
the diffusion process which gas molecules transfer from gas
phase to biofilm surface could provide sufficient time of this
55
diffusion process to degrade contaminants by biological flora
[12]. The diffusion of gas molecules restricted under shorter
EBRT condition because the biofilm could not deal with
excess gas molecules with enough react time that limited the 50
0.1 0.2 0.3 0.4 0.5
total removal efficiency of filter [26]. And when EBRT added Spray density (m3 ·m−2 h−1)
to a certain extent the changing curve trend of RE began
to be smooth due to the limitation of microbial degradation (a) 110 mg·m−3
(b) 200 mg·m−3
[3]. Compared with the RE of three inlet concentrations
(c) 300 mg·m−3
(200, 300, and 400 mg⋅m−3 ), group (a) and (b) showed higher
performance than group (c) possibly due to the limitation Figure 6: The effects of spray density on ethanethiol removal
of biological diffusion regime which may produce a exceed efficiency.
biomass accumulation. The results also indicated that a good
performance of degrading ET achieved by employing bio-
rickling filter, and about 70 s (superficial gas velocity of 8.74 × molecules inside diffusion with a result that microorganisms
10−3 m⋅s−1 ) was the best EBRT for the biotrickling filter. could not degrade ET successively or well. On the other
hand, due to both reasons of nutrient limitation and hardly
3.4. Effect of Spray Density on RE. The spray density was insoluble properties in water of ET (Henry coefficient: 0.15–
another key parameter in the biofiltration desulfurization 0.21) [1], the RE increased extremely little even if the spray
process [37]. The effect of spray density on RE was investi- density was added, generally, the RE hardly increased. And
gated under experimental condition of which the tempera- the optimum spray density of nutrient solution in this study
ture was 20–25∘ C and EBRT was 60 s. There were also three was 0.24 m3 ⋅m−2 h−1 .
groups studied under constant and variable gradient inlet
concentration (shown in Figure 6). It could be seen that an 3.5. Orthogonal Experiments. Three-factor and three-level
upper trend of removal efficiencies in each group presented orthogonal experiments were designed to decide the opti-
in Figure 6 was obtained with constantly increasing spray mized condition of biotrickling filter. The main three inves-
density. As Figure 6 shows, the ET REs of three groups (a), tigated factors of orthogonal experiment were spray density
(b), and (c) had greatly improved when the spray density was (0.08, 0.24, and 0.39 m3 ⋅m−2 h−1 ), EBRT (34.34, 68.67, and
less than 0.19 m3 ⋅m−2 h−1 ; correspondingly, stable tendency of 137.34 s), and inlet concentration (200, 300, and 400 mg⋅m−3 ).
REs of three groups was achieved when the spray density was The experimental result was shown in Table 1. According
greater than 0.19 m3 ⋅m−2 h−1 and the RE values were about to the range value of each factor, in present study situation,
60%. the affecting degree of each factor was spray density, inlet
Higher RE in biotrickling filter was found by increasing concentration, and EBRT. However, the optimized condi-
spray density probably mainly due to the metabolism of tion combined with previous experimental results could be
microorganisms [27–29]. The degradation process of ET determined as 0.24 m3 ⋅m−2 h−1 of spray density, less than
through biological flora fixed on inorganic ceramic needs
250 mg⋅m−3 of inlet concentration, and 68.7 s of the EBRT.
to obtain appropriate amount of nutrients from nutrient
However, the ethanethiol concentration after treatment by
solution to maintain normal metabolism and growth of
microorganisms [12]. So the amount of nutrients provided using the present biotrickling filter did not exceed 10.0 mg⋅L−1
by nutrient solution became a limitation to the speed of which was the maximum allowable concentration in an
metabolism of microorganisms. Thus increased spray density environment in regulations in this condition [2]. Thus, this
could stimulate the activity of microorganism metabolism study method was satisfying and was applied to remove low
because of the increase in the concentration of necessary concentration of ethanethiol. Besides, according to research
nutrients [29]. When the spray density added up to a by Huaxin et al. [31], the bottom layer removed more than
certain extent (0.24 m3 ⋅m−2 h−1 ), the moisture content of 50% of the target waste gas when the inlet concentration
packing materials surface would increase excessively and was lower than 70 mg⋅m−3 , but with the inlet concentration
then resulted in a growth formation of liquid membrane increasing to more than 90 mg⋅m−3 , the middle and upper
on microbial membrane [27]. However, intemperate growth layer played a major role for removal and the contribution of
and excessive thick liquid membrane could affect the ET gas the bottom decreased to 35%. Therefore, the higher RE could
6 Journal of Chemistry

Table 1: The result of orthogonal experiments.

−2 −1
Factor Spray density (m ⋅m h )
3
EBRT (s) Inlet concentration (mg⋅m−3 ) Outlet concentration (mg⋅m−3 ) RE (%)
1 0.08 34.34 200 86.62 56.69
2 0.08 68.67 300 133.14 55.62
3 0.08 137.34 400 182.08 54.48
4 0.24 34.34 300 113.91 62.03
5 0.24 68.67 400 159.88 60.03
6 0.24 137.34 200 71.78 64.11
7 0.39 34.34 400 159.81 60.05
8 0.39 68.67 200 71.74 64.13
9 0.39 137.34 300 109.89 63.37
Average 1 55.60 59.59 61.64
Average 2 62.06 59.93 60.34
Average 3 62.52 60.65 58.19
Range 6.92 1.06 3.45

probably reach more than 66% by using multilayer filler with bioreactor. An unobvious drop magnitude of ET removal
more than three layers. efficiency from 64.98% to 62.30% could be also seen.

3.6. pH Values and Metabolic Product Analysis. Because no 3.7. Kinetic Analysis. Biotrickling filter reactor was a kind
biotransformation exists to consume sulfate which was the of nonsubmerged gas phase bioreactor [38]. Based on the
major metabolic products [30] of ET in biotrickling filter, it research hypothesis that the microorganism fixed on inor-
would accumulate in the nutrient solution and the pH would ganic packing surface distributes evenly, the airstream mode
drop with an increase in operation time. The pH values and was plug-flow and oxygen condition was not a limitation
sulfate concentrations of nutrient solution for ET removal for biological aerobic respiration, consult relevant informa-
were regularly determined in biotrickling filter during 3- tion literature [38, 39], Michaelis-Menien equation was an
4-week operation period. And the results were shown in appropriate biological degradation mode for this studied
Figure 7. desulfurization process:
As Figure 7(a) shows, there was a linear relationship
𝑉𝑚 ⋅ 𝐶
between ET various inlet loads 𝑁V and sulfate concentration 𝑅𝑠 = , (6)
and pH values of nutrient solution. When the ET various inlet 𝐾𝑠 + 𝐶
loads 𝑁V (g⋅m−3 h−1 ) added from 7.39 to 11.34 g⋅m−3 h−1 , the
sulfate concentration ranged from 15.36 to 417.63 mg⋅L−1 , and where 𝑅𝑠 (g⋅m−3 d−1 ) is substrate utilization rates, 𝑉𝑚
pH values of nutrient solution dropped from 7.7 to 4.9. Thus (g⋅m−3 d−1 ) is the maxim removal rates, and 𝐶 (mg⋅m−3 )
sulfate SO4 2− produced in the biofiltration desulfurization is concentration of contaminant and 𝐾𝑠 is half-saturation
process was certain. After the values of pH added up to 5, constant in equation. A simplified equation (7) obtains by
there was no obvious change of trend of SO4 2− concentration linearizing the equation of Michaelis-Menien Mode through
even though various inlet loads 𝑁V added. That probably due Lineweaver-Burk:
to the weak alkaline ion besides SO4 2− such as S2− and SO3 2− 1 𝐾𝑠 1
produced in desulfurization process [3]. There were some = + , (7)
𝑅 𝑉𝑚 ⋅ 𝐶ln 𝑉𝑚
pale yellow substances with some characteristics of elemental
sulfur material produced in the reactor, which makes the where 𝑅 is removal rates of contaminant [𝑄(𝐶in − 𝐶ot )/𝑉]
function of spray liquid did not further acidification [37]. and 𝐶ln is log-average concentration of contaminant [(𝐶in −
In addition, the added concentrations of SO4 2− did not 𝐶ot )/ ln(𝐶in /𝐶ot )]. In addition, 𝐶in (mg⋅L−1 ) and 𝐶ot (mg⋅L−1 )
make a difference with pH values decreasing, indicating that are the inlet concentrations and the outlet concentrations of
the variation of pH nearly had no effect on the microbial gas compounds, respectively. 𝑄 (m3 ⋅h−1 ) is gas volume flow of
degradation of ET in biotrickling filter. gas compounds of ET. There the intercept and slope could be
Figure 7(b) was shown the relationship between removal calculated from a linear relationship between 1/𝑅 and 1/𝐶ln
efficiencies of ET and conversion of SO4 2− during the oper- by analyzing experimental data because they do represent 𝐾𝑠
ation period. The conversion rates of SO4 2− showed lower and 𝑉𝑚 .
trend at first with the maximum value of 99.62 mg⋅d−1 and the The experimental data of ET outlet concentration during
minimum value of 64.22 mg⋅d−1 under continuous operation constantly stable long-running regime in biotrickling filter
in biotrickling filter reactor, and then there was a slight system had been fitted with Michaelis-Menien model [39].
rise about 70–80 mg⋅d−1 . Therefore the conversion rate could And the running conditions were at a temperature of 25∘ C,
keep at a high level for a longtime-running regime in the inlet gas flow of about 0.15 m3 ⋅h−1 , and the filter volume of
Journal of Chemistry 7

1000 8 120 70

SO4 2− conversion rates (mg ·L−1)

800
SO4 2− concentration (mg ·L−1)

100
6

Ethanethiol RE (%)
600 80

pH
4 65
400
60

200 2
40

0
0 20 60
7 8 9 10 11 0 5 10 15 20 25
−3 −1
Inlet loads N (g·m h ) Running time (d)
2− 2−
SO4 SO4 conversion rates
pH Ethanethiol RE
(a) (b)

Figure 7: (a) The effects of ethanethiol inlet loads on sulfate ion concentration and pH and (b) continuous operation SO4 2− conversion rate
and ethyl mercaptan removal rate.

0.40 the spray density of 0.24 m3 ⋅m−2 h−1 , and the EBRT of 68.7 s.
And more than 64% of ET removal efficiency was achieved
y = 0.0359x + 0.0451 in that case. In addition, the main metabolic product was
0.35 R2 = 0.9754
SO4 2− under continuous long-running regime in filter, and
the concentration of SO4 2− increased with pH dropping due
to the increase of inlet loads. But both ranges of SO4 2− and
1/Rg (m3· d)−1

pH had no significant effect on ET removal performance. The

0.30
fitted experimental correlation coefficient 𝑅2 = 0.975, and
the kinetic degradation parameters 𝐾𝑠 = 7.96 mg⋅m−3 and
𝑉𝑚 = 221.73 g⋅m−3 h−1 . The ET desulfurization process could
0.25 better meet with the Michaelis-Menien model.

0.20
Conflict of Interests
6.0 6.5 7.0 7.5 8.0 8.5
1/Cln (g·m−3 )−1 The authors declare that there is no conflict of interests
regarding the publication of this paper.
Figure 8: Fitting result of biotrickling filter system for ethanethiol
removal.
Acknowledgments
The authors thank the financial support from Jiangsu Key
6.36 × 10−3 m3 . The fitted result was shown in Figure 8. The Laboratory of Atmospheric Environment Monitoring and
results showed that it could better meet the Michaelis-Menien Pollution Control of Nanjing University of Information
models by using biotrickling filter for the removal of ET. The Science and Technology, Jiangsu Province Innovation Plat-
correlation coefficient 𝑅2 was 0.975 that indicated a good form for Superiority Subject of Environmental Science and
correlation. Two kinetic parameters could be calculated as Engineering (no. KHK1203), and the Science and Technology
𝐾𝑠 = 7.96 mg m−3 and 𝑉𝑚 = 221.73 g⋅m−3 h−1 . Project of Anhui Province of China (no. 12010402097) for
supporting this study.
4. Conclusions
The desulfurization process of sulfur odor ET by microor- References
ganisms fixed on iron oxide-based porous ceramsite (IPC) [1] Y. Y. Li and L. X. Shi, “Comparison of GC-FPD and GC-FID in
in biotrickling filter was investigated. The results showed determining ethanethiol in air of workplace,” Chinese Journal
that the optimum running conditions of ET degradation of Health Laboratory Technology, vol. 23, no. 16, pp. 3190–3228,
were at the inlet concentration of less than 250 mg⋅m−3 , 2013.
8 Journal of Chemistry

[2] M. Sedighi, F. Vahabzadeh, S. M. Zamir, and A. Naderifar, the removal of ammonia and volatile organic sulfur compounds
“Ethanethiol degradation by Ralstonia eutropha,” Biotechnology (VOSCs),” Chemical Engineering Journal, vol. 152, no. 1, pp. 44–
and Bioprocess Engineering, vol. 18, no. 4, pp. 827–833, 2013. 53, 2009.
[3] A. M. Montebello, M. Fernández, F. Almenglo et al., “Simulta- [18] B. Sercu, D. Núñez, G. Aroca, N. Boon, W. Verstraete, and H.
neous methylmercaptan and hydrogen sulfide removal in the van Langenhove, “Inoculation and start-up of a biotricking filter
desulfurization of biogas in aerobic and anoxic biotrickling removing dimethyl sulfide,” Chemical Engineering Journal, vol.
filters,” Chemical Engineering Journal, vol. 200–202, pp. 237– 113, no. 2-3, pp. 127–134, 2005.
246, 2012. [19] S. Wan, G. Li, T. An, and B. Guo, “Co-treatment of single, binary
[4] E. Smet, P. Lens, and H. van Langenhove, “Treatment of waste and ternary mixture gas of ethanethiol, dimethyl disulfide and
gases contaminated with odorous sulfur compounds,” Critical thioanisole in a biotrickling filter seeded with Lysinibacillus
Reviews in Environmental Science and Technology, vol. 28, no. 1, sphaericus RG-1,” Journal of Hazardous Materials, vol. 186, no.
pp. 89–117, 1998. 2-3, pp. 1050–1057, 2011.
[5] K. Okada, T. Yamamoto, K.-H. Kim et al., “Removal of hydrogen [20] W.-B. Yang, W.-H. Chen, C.-S. Yuan, J.-C. Yang, and Q.-L.
sulfide with steelmaking slag by concurrent reactions of sulfide Zhao, “Comparative assessments of VOC emission rates and
mineralization and oxidation,” Ecological Engineering, vol. 63, associated health risks from wastewater treatment processes,”
no. 1, pp. 122–126, 2014. Journal of Environmental Monitoring, vol. 14, no. 9, pp. 2464–
[6] G. Muthuraman and M. Il-Shik, “Single catalyst of aqueous CoIII 2474, 2012.
for deodorization of mixture odor gases: a development and [21] Z.-B. Yue, H.-Q. Yu, H. Harada, and Y.-Y. Li, “Optimization of
reaction pathway study at electro- scrubbing process,” Journal anaerobic acidogenesis of an aquatic plant, Canna indica L., by
of Hazardous Materials, vol. 260, no. 1, pp. 1064–1072, 2013. rumen cultures,” Water Research, vol. 41, no. 11, pp. 2361–2370,
[7] S. Y. Yang, L. L. Wang, L. Y. Feng et al., “Wet scrubbing process 2007.
for methyl mercaptan odor treatment with peroxides: compar- [22] J. W. van Groenestijn and N. J. R. Kraakman, “Recent develop-
ison of hydrogen peroxide, perulfate and peroxymonosulfate,” ments in biological waste gas purification in Europe,” Chemical
Environmental Chemistry, vol. 33, no. 1, pp. 81–86, 2014. Engineering Journal, vol. 113, no. 2-3, pp. 85–91, 2005.
[8] D. C. Ding, G. Lu, P. Liu et al., “Photolysis and oxidation of [23] L. Arellano-Garcı́a, A. González-Sánchez, G. Baquerizo, S.
hydrogen sulfide gas using high-intensity UV spherical lamp,” Hernández-Jiménez, and S. Revah, “Treatment of carbon disul-
Chinese Journal of Environmental Engineering, vol. 6, no. 12, pp. fide and ethanethiol vapors in alkaline biotrickling filters using
4609–4614, 2012. an alkaliphilic sulfo-oxidizing bacterial consortium,” Journal of
[9] A. S. Stasinakis, “Use of selected advanced oxidation processes Chemical Technology and Biotechnology, vol. 85, no. 3, pp. 328–
(AOPs) for wastewater treatment: a mini review,” Global Nest 335, 2010.
Journal, vol. 10, no. 3, pp. 376–385, 2008. [24] M. Sedighi and F. Vahabzadeh, “Kinetic Modeling of
[10] G. Busca and C. Pistarino, “Technologies for the abatement cometabolic degradation of ethanethiol and phenol by
of sulphide compounds from gaseous streams: a comparative Ralstonia eutropha,” Biotechnology and Bioprocess Engineering,
overview,” Journal of Loss Prevention in the Process Industries, vol. 19, no. 2, pp. 239–249, 2014.
vol. 16, no. 5, pp. 363–371, 2003. [25] J. Hernández, J. Lafuente, Ó. J. Prado, and D. Gabriel, “Simulta-
[11] A. L. Cazetta, A. M. M. Vargas, E. M. Nogami et al., “NaOH- neous removal of H2 S, NH3 , and ethyl mercaptan in biotrickling
activated carbon of high surface area produced from coconut filters packed with poplar wood and polyurethane foam: impact
shell: kinetics and equilibrium studies from the methylene blue of pH during startup and crossed effects evaluation,” Water, Air,
adsorption,” Chemical Engineering Journal, vol. 174, no. 1, pp. & Soil Pollution, vol. 223, no. 6, pp. 3485–3497, 2012.
117–125, 2011. [26] Y. Jin, M. C. Veiga, and C. Kennes, “Effects of pH, CO2 , and flow
[12] T. C. An, S. G. Wan, G. Y. Li, L. Sun, and B. Guo, “Compar- pattern on the autotrophic degradation of hydrogen sulfide in a
ison of the removal of ethanethiol in twin-biotrickling filters biotrickling filter,” Biotechnology and Bioengineering, vol. 92, no.
inoculated with strain RG-1 and B350 mixed microorganisms,” 4, pp. 462–471, 2005.
Journal of Hazardous Materials, vol. 183, no. 1–3, pp. 372–380, [27] S. H. Li, B. Yan, F. Li et al., “Study on removal rate of methyl
2010. ercapatan and ethanethoil by bio-trickling filter,” Journal of
[13] X.-Q. Yang and B.-X. Tang, “Research and application status Natural Science of Heilongjiang Unversity, vol. 6, no. 22, pp. 724–
of biological deodorization technology,” Modern Agricultural 728, 2005.
Science and Technology, vol. 6, no. 1, pp. 297–298, 2006. [28] X. Y. Dong, Y. Zhao, and W. Kou, “Optimal operating conditions
[14] H. H. J. Cox and M. A. Deshusses, “Co-treatment of H2 S and for H2 S removal by an anoxic bio-trickling reactor,” Chinese
toluene in a biotrickling filter,” Chemical Engineering Journal, Journal of Environmental Engineering, vol. 7, no. 6, pp. 2373–
vol. 87, no. 1, pp. 101–110, 2002. 2377, 2012.
[15] Y. Jin, M. C. Veiga, and C. Kennes, “Co-treatment of hydrogen [29] J. Li, G. Ye, D. Sun, T. An, G. Sun, and S. Liang, “Performance of
sulfide and methanol in a single-stage biotrickling filter under a biotrickling filter in the removal of waste gases containing low
acidic conditions,” Chemosphere, vol. 68, no. 6, pp. 1186–1193, concentrations of mixed VOCs from a paint and coating plant,”
2007. Biodegradation, vol. 23, no. 1, pp. 177–187, 2012.
[16] Z. G. Xie, W. J. Guan, F. G. Ji, Z. Song, and Y. Zhao, “Production [30] B. Liu, A.-X. Jiang, Y.-X. Cheng, Z. Li, and B.-Q. Li, “Removal
of biologically activated carbon from orange peel and landfill of mixed H2 S-MT stench by trickled-bed biofilters connected in
leachate subsequent treatment technology,” Journal of Chem- series,” China Environmental Science, vol. 23, no. 6, pp. 618–621,
istry, vol. 2014, Article ID 491912, 9 pages, 2014. 2003.
[17] C. Hort, S. Gracy, V. Platel, and L. Moynault, “Evaluation of [31] Z. Huaxin, L. Shunyi, Y. Songbo et al., “Research on treatment
sewage sludge and yard waste compost as a biofilter media for of odor gas containing hydrogen sulfide by multilayer biofilter,”
Journal of Chemistry 9

Chinese Journal of Environmental Engineering, vol. 5, no. 1, pp.

157–160, 2011.
[32] Y. Q. Chen, Z. D. Fan, L. X. Ma, J. Yin, M. Luo, and W. F. Cai,
“Performance of three pilot-scale immobilized-cell biotrickling
filters for removal of hydrogen sulfide from a contaminated air
steam,” Saudi Journal of Biological Sciences, vol. 21, no. 5, pp.
450–456, 2014.
[33] M. T. Namini, N. Abdehagh, S. M. Heydarian, B. Bonakdarpour,
and D. Z. B. Kooki, “Hydrogen sulfide removal performance of
a bio-trickling filter employing Thiobacillus thiparus immobi-
lized on polyurethane foam under various starvation regimes,”
Biotechnology and Bioprocess Engineering, vol. 17, no. 6, pp. 1278–
1283, 2012.
[34] The Minister of Health of the People’s Republic of China,
GBZ/T160.49-2004 Methods for Determination of Mercaptans in
the Air of Workplace, Standards Press of China, Peking, China,
2004.
[35] The Minister of Health of the People’s Republic of China,
GB/T13025.8-91 General Test Methods in Salt Industry: Determi-
nation of Sulfate Ion, Standards Press of China, Beijing, China,
2004.
[36] S. Rappert and R. Müller, “Odor compounds in waste gas
emissions from agricultural operations and food industries,”
Waste Management, vol. 25, no. 9, pp. 887–907, 2005.
[37] S. Kim and M. A. Deshusses, “Understanding the limits of H2 S
degrading biotrickling filters using a differential biotrickling
filter,” Chemical Engineering Journal, vol. 113, no. 2-3, pp. 119–
126, 2005.
[38] H. X. Zhan, S. Y. Li, S. B. Yang et al., “Research on treatment
of odor gas containing hydrogen sulfide by multilayer biofilter,”
Chinese Journal of Environmental Engineering, vol. 1, no. 5, pp.
157–160, 2011.
[39] Y. Lu, J. Liu, B.-N. Lu, F. Li, and A.-X. Jiang, “Process perfor-
mance and kinetics of benzene and toluene waste-gas treatment
by biological method,” Chemical Engineering, vol. 7, no. 36, pp.
55–57, 2008.
 Photoenergy
International Journal of
International Journal of Organic Chemistry International Journal of Advances in
Medicinal Chemistry
Hindawi Publishing Corporation
International
Hindawi Publishing Corporation Hindawi Publishing Corporation
Analytical Chemistry
Hindawi Publishing Corporation
Physical Chemistry
Hindawi Publishing Corporation
http://www.hindawi.com Volume 2014 http://www.hindawi.com Volume 2014 http://www.hindawi.com Volume 2014 http://www.hindawi.com Volume 2014 http://www.hindawi.com Volume 2014

International Journal of

Carbohydrate Journal of
Chemistry
Hindawi Publishing Corporation
Quantum Chemistry
Hindawi Publishing Corporation
http://www.hindawi.com Volume 2014 http://www.hindawi.com Volume 2014

Submit your manuscripts at

http://www.hindawi.com

Journal of
The Scientific Analytical Methods
World Journal
Hindawi Publishing Corporation
in Chemistry
Hindawi Publishing Corporation
http://www.hindawi.com Volume 2014 http://www.hindawi.com Volume 2014

Journal of International Journal of International Journal of Journal of Bioinorganic Chemistry

Spectroscopy
Hindawi Publishing Corporation
Inorganic Chemistry
Hindawi Publishing Corporation
Electrochemistry
Hindawi Publishing Corporation
Applied Chemistry
Hindawi Publishing Corporation
and Applications
Hindawi Publishing Corporation
http://www.hindawi.com Volume 2014 http://www.hindawi.com Volume 2014 http://www.hindawi.com Volume 2014 http://www.hindawi.com Volume 2014 http://www.hindawi.com Volume 2014

Journal of  Chromatography   Journal of Journal of International Journal of

Theoretical Chemistry
Hindawi Publishing Corporation
Research International
Hindawi Publishing Corporation
Catalysts
Hindawi Publishing Corporation
Chemistry
Hindawi Publishing Corporation
Spectroscopy
Hindawi Publishing Corporation
http://www.hindawi.com Volume 2014 http://www.hindawi.com Volume 2014 http://www.hindawi.com Volume 2014 http://www.hindawi.com Volume 2014 http://www.hindawi.com Volume 2014