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DOI 10.1007/s10098-007-0141-4
ORIGINAL PAPER
Received: 10 September 2006 / Accepted: 3 February 2007 / Published online: 22 January 2008
! Springer-Verlag 2008
Introduction
Over the past few years, there has been increasing interest
towards biogas for energy production in cogeneration
plants, internal combustion engines and recently also in
fuel cells (Spiegel and Preston 2003, 2000; Spiegel et al.
1999). Its use for energy production is justified by the high
concentration of methane (4070 vol%) and encouraged by
several regulations aiming at the reduction of emissions.
Biogas is mostly produced by the digestion of organic
materials in waste disposal sites and sewage treatment
plants. Besides methane, this gas contains carbon dioxide
(3050 vol%), a lower percentage of N2, H2, CO and a
small amount of contaminants, responsible for damaging
equipments and requiring service interruptions and
expensive repairs. Specific contaminants to biogas utilization are hydrogen sulphide, halides and silicon-containing
compounds (volatile methyl siloxanesVMSs).
The concentration of VMSs in biogas (Schweigkofler and
Niessner 2001) depends on the source of biogas; landfill gas
is usually richer in siloxanes than fermentation gas and the
concentration can be up to 50 mg m-3. One of the most
common compounds is octamethylcyclotetrasiloxane (D4)
shown in Fig. 1. VMSs originate from hydrolysis of polydimethylsiloxane (PDMS) (Chandra 1997), an organosilicon
compound (Fig. 1) used in a wide range of consumer and
industrial applications, released into the environment
through landfills and wastewater treatment plants.
During combustion of biogas, siloxanes oxidize to SiO2.
These crystalline deposits can ultimately build a surface
thickness of several millimetres and they are difficult to
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F. Accettola et al.
Fig. 1 Polydimethylsiloxane
(PDMS) hydrolyzes to lower
molecular-weight compounds
(VMSs) like
octamethylcyclotetrasiloxane
(D4)
remove by chemical or mechanical means. They accumulate on pistons, cylinder heads and valves reducing
compression and engine efficiency. In a 1 MW engine
fuelled with a biogas flow rate of 240 Nm3 h-1 containing
only D4 with a concentration of 12 mg m-3 (1 ppmv),
silicates will generate up to 21 kg silicates per year, part of
which are deposited on the surfaces (Fig. 2) (Applied Filter
Technology 2003). The manufacturers of gas engines
introduced a limit value for silicon of 1 mg l-1 measured
in the oil of gas engines in order to prevent premature
engine failure due to silicon-induced damages (Prabucki
et al. 2001). Other limits imposed by engine manufacturers
refer to the content of methane. In this case the maximum
total siloxane concentration allowed might go down to less
than 10 mg Nm-3 methane (Environment Agency 2002)
(corresponding approximately to 5 mg Nm-3 biogas).
Silicate deposits can also result in poor heat transfer in heat
exchangers. In turbines, silicates can cause abrasions to the
blades. When using biogas in microturbines the limit
imposed is less than 10 ppb (Commonwealth Energy
Biogas 2004). Additionally, the glassy residues are
responsible for the inactivity of the catalyst of the emission
control system. The deposits clog the catalyst bed reducing
the availability of sites where the catalytic reaction occurs,
thus reducing the removal efficiency of combustion
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213
12.5 g
KH2PO4
3.8 g
(NH4)2SO4
MgSO4!7H2O
1g
0.1 g
FeSO4(NH4)2SO4!6H2O
0.232 g
0.174 g
0.116 g
CoSO4!7H2O
0.096 g
CuSO4!5H2O
8 mg
(NH4)6Mo7O24!4H2O
MnSO4!4H2O
0.022 g
8 mg
123
214
150 rpm at ambient temperature. The growth was monitored by optical density measurements at k = 270 nm
[wavelength related to nucleic acids (Alupoaei and Garcia-Rubio 2004)] and k = 600 nm using a Lambda 35
UV/VIS spectrophotometer (Perkin-Elmer, Austria) and
by measuring protein concentration with a protein test
according to the Bradford method, calibrating the method
by using bovine serum albumin (BSA) as standard. One
millilitre of homogenised sample (by using an Ultra
Turrax IKA T18 at 10,000 rpm for 2 min) was mixed
with 0.5 ml of a 0.3 N NaOH solution and heated up to
60"C for 90 min. Eventually, the samples were centrifuged and the supernatant was used for the determination
of the protein concentration. A protein assay kit was
purchased from Fluka (Austria). Optical density and
protein concentration were measured in duplicated and
homogenised samples.
123
F. Accettola et al.
Microorganism identification
Isolated bacteria have been identified in a first attempt, by
using API 20NE tests, purchased by bioMerieux GmbH,
and in a second attempt by 16S-rDNA-sequencing (analysis performed by Ecowork Laboratories Consulting
GmbH, Vienna, Austria). DNA was isolated from the
provided bacterial culture and used as a template for PCR
amplification of the 16S-rDNA. The obtained producta
mixture of the amplified 16S-rDNA-fragments of the bacteria in the culturewas cloned into plasmid pTZ57R/T;
48 single colonies were picked for RFLP analysis with the
restriction enzyme BsuRI of the cloned insert. Representative inserts from each restriction pattern were sequenced.
After editing, sequences were used for searches against
public databases (BLASTsearch).
215
G (m3 h-1)
EBRT (min)
D3 (mg m-3)
3.6
77
1.28
2.7
59
1.28
2.1
46
1.28
Biotrickling filter
Batch cultures
Batch cultures of series 2 showed at first an increase of the
optical density although values were very low (lower than
0.1 for OD600 and 0.4 for OD270). During this first period, it
was not possible to measure the protein content because of
some interference in the test, probably due to contaminants
in the sludge. These low values of OD were measured for a
period of six (for cultures with inoculum from Steyr
WWTP) and nine (inoculum from WWTP of silicon
123
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F. Accettola et al.
Bacteria identification
Degradation products
Based on measurements with the silicic acid test, no significant amounts of silicates were detected in any of the
samples (series 1). It may be possible that silicates were
mostly concentrated in the deposit obtained from the centrifugation. It can also be supposed that silicate interacts
with other intermediate reaction products not detectable as
free silicate or that the degradation does not end with the
formation of dissolved silicates.
The analysis of dimethylsilanediol (DMSD) in the cultures (series 1) revealed a concentration of 14 ppm when
compared to 7 ppm in the blank; therefore, D4 hydrolysis
was favoured by the presence of bacteria. Thus, biotic
123
Biotrickling filter
The removal efficiency of D3 [RE = (Cin - Cout)/Cin] and
elimination capacity [EC = (Cin - Cout) 9 Q/V, where
Cin is the inlet concentration, Cout the outlet concentration,
Q the gas flow and V the empty volume of the filter] have
been evaluated. During these first experiments, D4 was also
injected in the air stream by a continuous-flow syringe
pump; nevertheless, its concentration was not stable,
therefore no data about D4 degradation in the filter are
reported.
The gas flow rate was varied to check its influence in the
removal efficiency. As specified above, an increase in the
flow rate in this system causes a proportional decrease in
the D3 concentration to keep the organic load constant.
Operation of the biotrickling filter was started with a gas
flow rate of 0.5 l min-1 and an inlet D3 concentration of
77 mg m-3. As shown in Fig. 6a, relative high values of
RE and EC occurred when starting the experiment, probably because of some adsorption effect on the packing
material. During the following days, the RE was quite
stable between 10 and 20% while the EC was around
0.2 g m-3 h-1. The peaks in the graphs (days 2, 14, 30,
44) correspond to the substitution of the medium with fresh
one; hence it is possible that the higher values are due to a
major effect of absorption and to better nutritional conditions for the bacteria. After about 35 days though, the
efficiency decreased at values lower than 10%, excluding
217
Conclusions
Siloxane biodegradation has been investigated in order to
evaluate the possibility of using a biofiltration system to
treat biogas.
Results show that octamethylcyclotetrasiloxane can be
biodegraded by a community of microorganisms isolated
from activated sludge. Pseudomonas was identified as the
predominant genus in the mixed population while other
microorganisms found included Rhodanobacter, Zooglea,
Mesorhizobium and Xanthomonadacea. Furthermore,
DMSD, the degradation product of D4, has been found in
bacterial cultures in a higher concentration than in the
corresponding blank. A biotrickling filter was set up for the
treatment of an air stream polluted with siloxane. The
results obtained showed a removal of 1020% D3, while
the same system in abiotic conditions reported no removal
at all.
The present work on siloxane biodegradation and further
optimisation of the process (in regards to the biofilter setup and the determination of microbiologic parameters)
would give an important contribution to an issue which, so
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218
far, has been hardly addressed and about which very few
data are available from literature. The major aim would be
the development of a low-cost unit able to upgrade biogas
by biological means, thus encouraging its use for power
generation. Biofiltration has been proved a viable, low-cost
option for facilities having emissions that qualify for this
technology. It has been applied successfully for odour
control, treatment of air contaminated with hydrocarbons
or other pollutants, and, in regards to H2S, for biogas
upgrading. Its application for siloxane removal would be an
interesting cost-effective and environmentally friendly
alternative to present technologies for avoiding damage to
equipment and increase of CO and NOx emissions in biogas-fuelled power plants.
Acknowledgments This work has been carried out with the financial support of European Community (Marie Curie Host Fellowship).
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