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Hydrogen Sulfide Removal From Biogas by Biotrickling Filter Inoculated With Halothiobacillus Neapolitanus
Hydrogen Sulfide Removal From Biogas by Biotrickling Filter Inoculated With Halothiobacillus Neapolitanus
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Article history: Hydrogen sulfide (H2S), a highly corrosive gas, is found in biogas due to the biodegradation
Received 17 March 2017 of proteins and other sulfur containing organic compounds present in feed stock during
Received in revised form anaerobic digestion. The presence of H2S is one of the biggest factors limiting the use of
29 April 2017 biogas. It should be removed prior to application of biogas in an electric generator or in-
Accepted 2 May 2017 dustrial boiler. The present research evaluated the performance of biotrickling filter
Available online xxx inoculated with Halothiobacillus neapolitanus NTV01 (HTN) on the H2S removal from syn-
thetic biogas. HTN, isolated and purified from activated sludge, is a sulfur oxidizing bac-
Keywords: teria able to degrade H2S and thiosulfate to elemental sulfur and sulfate, respectively.
Hydrogen sulfide Operational parameters in a short term operation were varied as following; gas flow rate
H2S (0.5e0.75 LPM); EBRT (40e120 s); the inlet H2S concentrations (0e1500 ppmv); liquid recir-
Biotrickling filter culation rate (3.6e4.8 L/h). EBRT showed a greater effect to the removal efficiency than
Halothiobacillus neapolitanus increasing H2S concentration. Longer EBRT resulted higher removal efficiency. The changes
Biogas of liquid recirculation rates did not significantly affect the removal efficiency. In long term
operation, the gas flow rate and liquid recirculation rate were fixed at 0.5 LPM (120 s EBRT)
and 3.6 L/h; and H2S concentrations were varied (0e2040 ppmv). The maximum elimina-
tion capacity was found as 78.57 g H2S/m3 h, which had greater performance than the
previous studies.
© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
* Corresponding author.
** Corresponding author. The Biosensor and Bioelectronics Technology Centre, King Mongkut's University of Technology North Bangkok,
Bangkok 10800, Thailand.
E-mail addresses: siriorn2002@yahoo.com (S. Boonyawanich), nipon.p@sci.kmutnb.ac.th (N. Pisutpaisal).
http://dx.doi.org/10.1016/j.ijhydene.2017.05.020
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article in press as: Vikromvarasiri N, et al., Hydrogen sulfide removal from biogas by biotrickling filter inoculated with
Halothiobacillus neapolitanus, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.020
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e9
Please cite this article in press as: Vikromvarasiri N, et al., Hydrogen sulfide removal from biogas by biotrickling filter inoculated with
Halothiobacillus neapolitanus, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.020
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e9 3
the packing media on which TMM was continuously spayed on Analytical techniques
the packing media. Air flow rate and liquid recirculation rate
were fixed at 0.5 LPM and 3.6 L/h. Fresh TMM as recirculating Growth of HTN was observed with colony forming unit
liquid was changed every 48 h, and pH was daily adjusted to 7 (CFU/ml) by drop plate technique [12]. pH was monitored by
[11]. The packing media were dried and weighed at the end of pH meter (Mettler Toledo FE20, Germany). Sulfate concentra-
each experiment. The growth of HTN and elemental sulfur tion was determined by turbidimetric method according to
production were determined by calculation of the weight dif- standard method [13]. Gas composition were measured both
ference between the beginning and the end processes. Recir- inlet and outlet gas concentrations by the GFM416 biogas an-
culating liquid was periodically collected to measure pH, cell alytic handheld instrument (Gas Data, England).
number, temperature, and sulfate concentration.
The synthetic biogas (60% methane and 40% carbon dioxide Immobilization process
were mixed with 5000 ppmv H2S) was used as an inlet gas to the
biotrickling filter. All gas tanks have valves, pressure gauges, HTN was successfully immobilised on the packing media.
and flow meters to control the gas flow rates. This synthetic TMM, recirculating liquid, was changed every 48 h, and pH
biogas was mixed with air (>3% v/v), pumped through a 0.2 mm was adjusted to 7 every 24 h (Fig. 2). The experiments were
syringe filter and controlled by flow meter. The mixed gas was conducted at room temperature (31.5 ± 1.5 C). pH was
introduced upward into a packed bed. The gas flow rate was controlled in the range of 6.12e7.00. The results showed that
varied from 0.5 to 0.75 LPM. EBRT and H2S concentrations were the number of HTN in liquid phase did not change even when
varied in the range of 40e120 s, and 0e1500 ppmv. the medium was replaced as in the immobilization experi-
This study preferred to use energy sources derived from ment. The average of suspended cells in the recirculating
only oxidation for microorganism growth, so Na2S2O3$5H2O in medium was 8.59 107 CFU/mL. The average of sulfate pro-
the liquid medium in the recirculation tank was removed after duction rates was 112 ± 11 mg/L h. The results of pH changes
immobilization process. TMM was pumped to the upper apparently corresponded with sulfate production. The sulfate
packaging media, and then it was recirculated during the concentration after 48 h of operation of each medium was
experiment. The liquid recirculation rate was varied from 3.6 similar with an average of 5390 ± 570 mg/L. The results of the
to 4.8 L/h. The experiments were operated at room tempera- immobilization experiments were not significantly different
ture 32e36 h. Samples were collected and analyzed as previ- in each experiment.
ously mentioned. Elemental sulfur was vividly accumulated on the media
In abiotic experiment, synthetic biogas with inlet gas H2S (Figs. 3 and 4). This result is different from the previous report.
concentration of 100 ppmv was used. Air flow rate and liquid Wood et al. (2005) reported that HTN produces sulfur when pH
recirculation rate were 0.5 LPM and 3.6 L/h, respectively. is lower than 5 [9]. However, the present research found that
HTN can produce elemental sulfur even at pH 6 or higher.
H2S removal under long-term operation
Effect of H2S loading rate on H2S removal
The synthetic biogas flow rate was 0.5 LPM with EBRT of 120 s,
and H2S concentrations were varied 0e2040 ppmv. The liquid The increase of the H2S loading rate can be increased by
recirculation rate was 3.6 L/h. The experiments were operated increasing inlet H2S concentrations. Fig. 5 showed the rela-
at room temperature for 126 h. tionship between H2S loading rate and the elimination
Fig. 2 e pH, suspended cells and sulfate concentration during the immobilization process.
Please cite this article in press as: Vikromvarasiri N, et al., Hydrogen sulfide removal from biogas by biotrickling filter inoculated with
Halothiobacillus neapolitanus, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.020
4 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e9
Fig. 3 e HTN and elemental sulfur accumulation on packing media in biotrickling filter during the immobilization process.
Fig. 5 e Relationship between H2S loading rate and elimination capacity (EC) at varying empty bed resident time.
Please cite this article in press as: Vikromvarasiri N, et al., Hydrogen sulfide removal from biogas by biotrickling filter inoculated with
Halothiobacillus neapolitanus, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.020
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e9 5
Fig. 6 e Removal efficiency at varying H2S inlet concentration and empty bed resident time.
capacity by varying EBRT. The elimination capacity is equal to removal efficiency. However, the EBRT reduction caused a
the loading rate, which results in the complete H2S removal greater effect to the removal efficiency than the increase of
(slope ¼ 1) [14]. The results showed that the highest slope H2S concentration (Fig. 6). Even the inlet concentration in
occurred at 120 s EBRT (slope ¼ 0.915), whereas the lower EBRT EBRT 120 s reached 1060 ppmv, the removal efficiency (92.92%)
(40, 60 and 80 s) had lower slope (0.793, 0.718 and 0.490, was higher than the removal efficiency at inlet concentration
respectively). There are two steps in the H2S removal in bio- 65 ppmv in all of lower EBRT (40, 60 and 80 s), which were
trickling filter. The first step, H2S in gas phase is removed by 92.31, 77.27 and 61.54%. The results found that at fixed H2S
diffusion into the liquid phase (Eq. (1)), and is metabolized by concentration, higher EBRT will have higher removal effi-
the microorganisms in the subsequent step (Eqs. (2)e(4)) [15]. ciency. At inlet concentration about 1500 ppmv, the remove
efficiency at 120 s EBRT was 87.46%, whereas the removal ef-
H2 S4HS þHþ ðnon biologicalÞ (1)
ficiency of lower EBRT were 67.21, 60.45 and 40.33%, respec-
tively. Therefore, the suitable EBRT for long term experiment
HS þ 0:5O2 /S0 þOH ðbiologicalÞ (2)
is 120 s (The gas flow rate is 0.5 LPM).
In addition, the oxygen consumption is this process was
HS þ 2O2 /SO2
4 þH
þ
ðbiologicalÞ (3)
0.1% v/v with the inlet concentration of 1.1e1.3% v/v. There-
þ
fore, the oxygen was not limited in this process. The inlet
2H2 S þ 3=2O2 /SO2
4 þH ðbiologicalÞ (4)
gases concentrations of methane and carbon dioxide were in
The lower retention time reduced the removal efficiency, the range of 54.6e39.9% v/v and 44.3e29.8% v/v. Both gases
which probably occurs from slow H2S diffusion from gas were negligibly affect by the biotrickling filter process,
phase into the liquid phase [16]. methane concentration was increased 0.1e0.3% v/v, and car-
Both the increase of the synthetic biogas flow rate (EBRT bon dioxide concentration was reduced 0.1e0.4% v/v. How-
reduction) and H2S concentration lead to the decreasing of the ever, two probable reasons for the carbon dioxide reduction
Fig. 7 e Relationship between the elimination capacity (EC) and H2S loading rate (LR) at varying the liquid recirculation rates.
Please cite this article in press as: Vikromvarasiri N, et al., Hydrogen sulfide removal from biogas by biotrickling filter inoculated with
Halothiobacillus neapolitanus, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.020
6 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e9
Fig. 8 e Relationship between inlet H2S concentration, removal efficiency and sulfate production in long term experiment.
were the consumption of microorganism (HTN) and the car- removal of metabolites, and biofilm moistening. Moreover, it
bon dioxide dissolution into liquid medium. Carbon dioxide is helped to remove the sulfuric acid from the filter bed. Besides,
slightly soluble in water (0.038 mol/L at pH 7 and 20 C), and the flow of liquid recirculation affected the performance sys-
the solubility will decrease with temperature. Moreover, only tem of the formation and the thickness of the biofilm in the
a small fraction of about 1% of the dissolved carbon dioxide biotrickling filter. Therefore, it can affect the maximum elim-
will be converted to H2CO3, which can be converted to car- ination capacity.
bonic acid (pK ¼ 6.35) [17]. In this research, the liquid recirculation rate varied from
3.6 to 4.8 L/h. The EBRT in this experiment was 120 s. The
Effect of liquid recirculation rate on H2S removal results showed that the removal efficiency of liquid recircu-
lation rates (3.6e4.8 L/h) were not significantly different by the
The liquid recirculation medium was used to control physio- gradients of the relationship between H2S loading rate and
logical conditions in the liquid phase of the biotrickling filter elimination capacity, which were 0.915 (3.6 L/h) and 0.907
system such as pH, nutrient supply, contamination absorption, (4.8 L/h) (Fig. 7). At the inlet H2S concentration about
Fig. 9 e HTN and elemental sulfur accumulation on packing media in biotrickling filter.
Please cite this article in press as: Vikromvarasiri N, et al., Hydrogen sulfide removal from biogas by biotrickling filter inoculated with
Halothiobacillus neapolitanus, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.020
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e9 7
References
removal efficiency. The liquid recirculation rate at 4.8 L/h
This study
the gas flow meter before being introduced to the biotrickling
filter. Moreover, Jin et al. (2005) reported that the higher liquid
flow rate caused the lower gradient. The degradation of
pollutant will be lower when decreasing the liquid residence
capacity (g H2S/m3 h)
time (increasing its flow rate) at the constant EBRT because
H2S elimination
the increase of the thickness of the liquid phase at a higher
liquid flow rate caused the limitation of mass transfer [16].
19.24
14.58
32.33
78.57
In addition, the average of suspended cells in liquid recir-
32.5
23.7
24
culation and sulfate production rate in gas running phase
(4.94 107 CFU/mL and 11 ± 0.4 mg/L h.) were lower than in
the immobilization process (8.59 107 CFU/mL and
112 ± 11 mg/L h). These results indicated that thiosulfate in
the medium was replaced by H2S in the gas running phase,
Halothiobacillus neapolitanus
Desulfurization bacteria
which affected the number of suspended cells and sulfate
Microorganism
Thiobacillus thioparus
Activated sludge
Activated sludge
thiosulfate can completely dissolve into medium.
(Indigenous)
Abiotic process test
Synthetic biogas was used as the inlet gas with H2S concen-
Table 1 e Comparison of the H2S elimination capacity of this study with previous reports.
þ
H2 S þ 2O2 /SO2
4 þ 2H DG0 ¼ 798:2 kJ=reaction (5)
BioSulfidEx
Glass ring
Lava rock
HDPE
þ
S0 þ H2 O þ 1½O2 /SO2
4 þ 2H DG0 ¼ 587:1 kJ=reaction (7)
10.29e72 min
12.71e31.77 s
0.17e1.17
0.5e0.75
0.2e0.5
(0.8423 g/L).
In addition, the inlet gases concentrations of methane,
carbon dioxide and oxygen were about 53.8 ± 0.1, 44.8 ± 0.1
and 1.2 ± 0.1% v/v in the abiotic experiment. The results found
H2S (ppmv)
1000e4000
100e2000
0e2040
10e90
0e190
H 2S þ N 2
Biogas
Gas
Please cite this article in press as: Vikromvarasiri N, et al., Hydrogen sulfide removal from biogas by biotrickling filter inoculated with
Halothiobacillus neapolitanus, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.020
8 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e9
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Please cite this article in press as: Vikromvarasiri N, et al., Hydrogen sulfide removal from biogas by biotrickling filter inoculated with
Halothiobacillus neapolitanus, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.020
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Halothiobacillus neapolitanus, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.020
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