Chemosphere 72 (2008) 16591663

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Decomposition of hexamethylcyclotrisiloxane over solid oxides

Elisabetta Finocchio a,*, Gilberto Garuti b, Marco Baldi c, Guido Busca a
a
b
c

Dipartimento di Ingegneria Chimica e di Processo, Facolt di Ingegneria, Universit di Genova, Pl.e Kennedy 1, 16126 Genova, Italy
Ecodeco SpA, Cassinazza di Baselica, 27010 Giussago (PV), Italy
Dipartimento di Chimica, Universit di Pavia, Viale Taramelli 12, I-27100 Pavia, Italy

a r t i c l e

i n f o

Article history:
Received 28 February 2008
Received in revised form 15 May 2008
Accepted 16 May 2008
Available online 7 July 2008
Keywords:
Cyclosiloxanes decomposition
Biogases cleaning
Hexamethylcyclotrisiloxane
Alumina adsorbent
Silica adsorbent
Calcium oxide adsorbent

a b s t r a c t
The decomposition of hexamethylcyclotrisiloxane (HMCTS) has been studied at room temperature and in
the range 473673 K over the surface of basic (CaO, MgO) and acidic oxides (Al2O3, SiO2). Alumina allows
the complete removal of HMCTS from synthetic biogases at 673 K. A reactive adsorption occurs with surface silication and release of methane. The adsorption capacity of our alumina adsorbent (180 m2 g1),
until saturation, at 673 K, is 0.31 g (HMCTS) g(Al2O3)1, which corresponds to one silicon atom per 9 2, i.e.
the silication monolayer capacity.
On the contrary, silica, which is an excellent adsorbent for siloxanes at room temperature, looses its
adsorption ability at high temperature as it is typical of a molecular adsorption behavior. Basic oxides
such as MgO and CaO have strong reactivity in decomposing siloxanes in the absence of CO2, but loose
reactivity when in contact with carbon dioxide because of surface carbonation.
2008 Elsevier Ltd. All rights reserved.

1. Introduction
Linear and cyclic polymethylsiloxanes are widely used in the
formulation of household, personal care and other industrial products (Wheless and Pierce, 2004; NIH, 2006). Cyclic oligomers are
also stable thermal degradation products of polydimethylsiloxane,
a member of the silicones family, being further decomposed only at
very high temperatures (Bogatyrov and Borysenko, 2000; Camino
et al., 2001). As a consequence, low molecular weight siloxanes are
commonly found in biogases produced in waste disposal sites and
waste water treatment plants. Silicon compounds represent noxious contaminants of biogases used as a fuel, because they may depose at the surface of fuel cell electrodes and combustion or steam
reforming catalysts, deactivating them, and are converted upon
combustion into quartz and silicate powders, which damage the
inner surfaces of the combustion engines and pollute the waste
gases. Their removal can be effectively achieved by condensation,
gas liquid extraction (sulphuric acid or nitric acid) or by solid phase
adsorption over activated charcoal, resins, molecular sieves and silica gel. Schweigkoer and Niessner (2001) made a comparative
study of adsorption materials using polymers, silica gel and activated carbon. In their tests all the adsorbent exhibited large
adsorption capacities for decamethylcyclopentasiloxane. Silica gel
seemed to be promising and a highly cost effective candidate for
* Corresponding author. Tel.: +39 010 3536027; fax: +39 010 3536028.
E-mail address: elisabetta.nocchio@unige.it (E. Finocchio).
0045-6535/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2008.05.032

application in gas treatments, since this material can be used

simultaneously for biogas drying. The desorption efciency of silica
gel can be up to 95% when heated at 523 K. Similar studies using
activated carbons as adsorption material showed a less effective
thermal regeneration (Dewil et al., 2006). According to a recent
patent (Higgins, 2006) activated alumina is also a good adsorbent
for siloxanes. A system containing two or more beds of activated
alumina can be used to remove siloxanes from biogas while regenerating one of the other beds. Lee et al. (2001) compared the
adsorption capacities of octamethylcyclotetrasiloxane from a
sludge biogas by adsorption on activated carbon, molecular sieve
13 and alumina, and found alumina the most efcient adsorber,
with a small loss in adsorbing capacity following regeneration by
desorption at 573 K. Basic oxides, such as CaO, has proven to be
interesting adsorbent for environmental applications even for high
temperature treatment (Orio et al., 1997), but, to our knowledge,
their reactivity in this specic application has not been tested
yet. In the frame of an investigation on the best procedures for biogas purication, we investigated the adsorption and thermal
decomposition of siloxane compounds over solid oxides and their
possible molecular degradation mechanism. In this work the
adsorption and conversion of hexamethylcyclotrisiloxane (Me2SiO)3 (HMCTS) over the surface of oxides having a basic (MgO,
CaO), an acidic (Al2O3, SiO2) character has been studied in static
and dynamic condition, focusing on the high temperature decomposition. Mineralization of silicon atoms at high temperature, as an
alternative approach to gas purication by room temperature

E. Finocchio et al. / Chemosphere 72 (2008) 16591663

adsorption, may be of interest when the gas has to be heated, e.g.

when the gas must be used in steam reforming to produce H2 and
further CO2. In these conditions, siloxane can be decomposed
above 473 K, producing methane and silica-like or silicates materials: the resulting materials may be disposed or used, e.g. in the cement industry.
2. Material and methods
The oxide adsorbents used in this study are listed in Table 1.
Flow tests have been performed in the line schematised in Supporting information 1, with a xed bed tubular quartz adsorber
reactor, lled with 1.3 g of adsorbent material in pellets (alumina),
powder (silica gel) or roughly ground pellets (calcium compounds).
The adsorbents were exposed to a ow of a synthetic biogas
(CO2:CH4, 44:56% v/v) saturated at room temperature with HMCTS
(corresponding to about 1.1% v/v) and water vapor using two bubblers. Total ow rate was 60 ml min1, corresponding to a contact
time around 2 s. Tests have been performed at 523 and 573 K.
Analysis of the reactants and reaction gaseous products have been
performed by on line FT-IR instrument (Thermosher Nicolet
6700) equipped with a gas cell connected to the adsorption apparatus and operating with OMNICTM Series acquisition software. A
full gas phase spectrum was recorded every 4 s, the sensitivity
was evaluated to be 1 ppm. Siloxanes consumption in the gas
phase has been evaluated by monitoring the intensity of the CH
stretching mode bands around 2970 cm1, the SiC stretching
mode bands around 1265 cm1, and the CH3 rocking mode bands
in the range 845818 cm1 (Handke and Jastrzebski, 2004). Methane concentration was monitored using of the CH4 stretching and
bending modes, corresponding to rotovibrational bands at 3016
and 1305 cm1. CO and CO2 were monitored using the rotovibrational CO stretching modes at 2143 cm1 and at 2345 cm1,
respectively. The analysis of water was made on the basis of the
rotovibrational bending mode at 1595 cm1.
Static adsorption experiments have been reported in a pyrex
glass reactor (Supporting information 2). The pure (fresh) powders have been pressed into self-supporting disks (40 mg) and
placed in the sample holder of the reactor connected to a conventional gas manipulation apparatus. Before any adsorption experiment, the powder has been activated by treating in high vacuum
(102 Pa) for 30 min at 473 K, in order to desorb water and weakly
held contaminants. The adsorption experiments have been carried
out at room temperature, by contacting the disks with siloxane vapors (partial pressure <133.3 Pa) in the cell. KBr windows allow the
IR analysis of the gas and of the adsorbent disk using a Thermoquest Nexus 750 FT-IR instrument. The glass sample holder, also
containing a magnet, was displaced from the sample-in-furnace
position to the sample-on-beam position using an external magnet. The spectra of both the disks and the gas phases have been
evaluated in the temperature range 473673 K.
After both static and dynamic adsorption experiments, the
oxide disks (spent adsorbents) have been extracted from the
apparatus, nely ground and diluted with KBr (in air), in order to
record the skeletal IR spectrum of the spent material and compare
it with that of the fresh one.

3. Results and discussion

3.1. Flow reactor studies of hexamethylcyclotrisiloxane (HMCTS)
adsorption and decomposition from synthetic biogas
In Fig. 1 the curves of the outlet gas phase concentration of
HMTCS using an alumina bed are reported. The experiments have
been performed with and without water vapour at 523 K and with
water vapour at 673 K. In all cases, the gas phase concentration of
HMTCS, measured by the absorbance (A) of the specic IR bands
of HMTCS, sharply decreased just after switching the ow from
the by-pass into the bed. Absorptiondesorption of HMCTS on the
walls of the tubes slows down the stepwise decrease of HMTCS concentration. In dry reaction conditions, HMCTS disappeared from
the ow (100% removal efciency) for about 37 min at 523 K, corresponding to 0.24 g of siloxane per gram of alumina, thus
1.3  103 g m2. Co-feeding water vapor in the feed gave rise to
a competitive effect towards siloxane adsorption, strongly reducing
alumina adsorption capacity around 0.05 g (HMCTS) g(Al2O3)1. At
673 K, 100% removal capacity was maintained for 49 min even in
the presence of water vapor, corresponding to 0.31 g (HMCTS)
g(Al2O3)1 (thus 1.7  103 g m2). Taking into account the surface
area of the adsorbent, the amount of HMTCS adsorbed on alumina
corresponds to one Si atom per 9 2, which corresponds roughly
to the monolayer coverage, i.e. the theoretical density of a silica
layer covering the alumina surface. Under these conditions, it has
also been possible to detect in the downstream a small but signicant increase in the intensity of the methane IR peaks, starting few
minutes after the switch from the by-pass to the reactor. Methane
results from the hydrolysis of the SiC bonds.
The spent adsorbent, once removed from the reactor, has been
analyzed by skeletal FT-IR spectroscopy. c-Aluminas characteristic
adsorptions are in the range 800500 cm1 (see Fig. 2a), The spectrum is clearly modied following high temperature HMCTS
adsorption. The spectrum recorded after the test at 523 K in the
presence of water (Fig. 2b) shows a new and broad adsorption
about 1050 cm1 and a weak component at 807 cm1 we assigned
to silica-like species. The modications of the spectrum below
800 cm1, namely the increased intensity of the component at
580 cm1, due to AlO stretching modes with Al ions in octahedral
coordination, suggest the formation of amorphous oxides (Busca
and Resini, 2000). This effect can explain the loss in adsorption efciency of alumina we detected in these experimental conditions.
On the other side, spectra of alumina recorded after the test at
673 K in the presence of water (Fig. 2c and d), relative to two samples taken from different positions in the bed) are typical of c-

2.0
1.8
1.6
523 K (with H2O)

1.4

A (a.u.)

1660

1.2
523 K, dry

1.0

673 K (with H2O)

0.8
0.6
0.4

Table 1
Main characteristics of oxide adsorbents
Surface area (m2 g1)

Crystalline phase
MgO
CaO
Al2O3
SiO2

0.2

Periclase
Cubic
c-Al2O3
Silica gel

31
3040
180
296

Commercial
Ex-CaCO3 calcination
Commercial Akzo
Commercial C.Eerba

0.0
0.00

50.00

100.00

150.00

200.00

t (min)
Fig. 1. HMCTS removal curves for alumina at 523 and 673 K (1% HMCTS/CH4/CO2,
dry or with water vapor fed).

1661

E. Finocchio et al. / Chemosphere 72 (2008) 16591663

behavior was observed for MgO material, whose siloxane adsorption capacity was almost zero.

0.40

a
b
0.26
1600

1400

1200

1000

800

600

Wavenumbers (cm-1)
Fig. 2. FT-IR spectra (KBr pressed disks) of the fresh alumina adsorbent (a) and the
spent adsorbent following contact tests at 523 K (b), 673 K (reactor top fraction) (c),
673 K (reactor bottom fraction) (d), humid conditions.

Al2O3 over which a silica-like or silicoaluminate phase is grown.

This phase is identied on the basis of the SiOSi asymmetric
stretching bands at 1205 (shoulder) and 1050 cm1. As expected,
the top fraction of the adsorbent bed, where the ow comes in, is
heavily silicized, while the amount of silica deposition lowers in
the bottom part of the reactor. In all the spectra residual SiC containing species are still detectable, revealed by the weak sharp
band at 1250 cm1. Another weak band at 1375 cm1, assigned
to CH3 deformation mode, can be taken as an indication of some
molecularly adsorbed siloxane at the surface.
Nevertheless, these data show that high temperature adsorption of HMCTS on alumina is predominantly reactive, with hydrolysis of SiC bonds and deposition of a silica layer on the adsorbent.
Silica gel has also been evaluated for high temperature siloxane
reactive adsorption, but this material, although very active in room
temperature HMCTS adsorption, 0.76 g of adsorbed siloxane per
gram of silica (corresponding to 2.5  103 gHMCTS m2), lost almost completely its efciency at 673 K (Fig. 3). This behaviour
agrees with a molecular adsorption mechanism, hindered for thermodynamics at high temperature.
In Fig. 3 results obtained in the same conditions (i.e. humid conditions) over CaO, CaO/CaCO3 and CaCO3 materials are also reported. The siloxane removing efciency from the owing biogas
at 523 K is about 0.003 g of adsorbed siloxane per gram of CaO/
CaCO3, corresponding to 1  104 gHMCTS m2. The skeletal IR
spectra of the spent adsorbent (not reported here) do not show
any signicant formation of silica or silicate species. The same

= 0.5 a.u.

Absorbance

Experiments of adsorption of HMCTS over solid oxides have

been performed in static conditions in a pyrex glass reactor/cell,
to have information on the chemistry of the phenomenon. Blank
experiments have been performed, by analysing siloxane vapour
decomposition in the empty IR cell at increasing temperatures,
both in dry conditions and in the presence of water vapor. No siloxane conversion has been detected up to 673 K.
The spectrum of pure c-alumina activated at 473 K (Fig. 4a)
shows the typical cut-off at low frequencies (around 1000 cm1)
due to skeletal absorption and a broad band in the region 3800
3200 cm1 due to OHs interacting with H-bond. This spectrum is
completely consistent with what we expect at such a low activation temperature (Busca et al., 1993). Adsorption of HMTCS and
heating at 473 K (Fig. 4b), led to the detection of bands at 2965
and 2907 cm1 (CH stretching modes), 1413 cm1 (CH deformation
mode), and 1260 cm1 (SiC deformation mode). These frequencies are only slightly shifted with respect to the spectrum of the
pure compound indicating a molecular interaction with the surface. At 473 K an intense absorption grows in the region 1200

Absorbance

Absorbance

Absorbance

3.2. Reactivity of hexamethylcyclotrisiloxane (HMCTS) at the surface of

metal oxides: Static adsorption experiments

2200

3800
3600
Wavenumbers (cm-1)

= 0.02 a.u.

2100
2000
1900
Wavenumbers (cm-1)

d
c
b
Al2O3
cut-off

a
4000

3500

3000

2500

2000

1500

Wavenumbers (cm-1)
Fig. 4. FT-IR spectra of c-Al2O3 outgassed at 473 K (a), and following contact with
HMCTS vapor at 473 K (b), 573 K (c) and 673 K (d). Inset A: subtraction spectrum
(b)(a). OH stretching region; Inset B: enlargement of silica overtones spectral
region.

2.5
CaO, 523 K

A(a.u.)

SiO2, 673 K

CaCO3

1.5

CaO/CaCO3

1
SiO2, 300 K
0.5

0
0

50

100

150
t (min)

200

250

10

15

20

25

30

35

40

45

50

t (min)

Fig. 3. HMCTS removal curves for silica (1% HMCTS/CH4/CO2/water vapor) at room temperature and at 673 K (dotted line) and for CaO/CaCO3 (1% HMCTS/CH4/CO2/water
vapor) at 523 K.

1662

E. Finocchio et al. / Chemosphere 72 (2008) 16591663

1000 cm1, which shift the cut-off limit of this sample towards
higher frequencies, as evidenced in Fig. 4. Bands in this region
are again typically due to SiOSi asymmetric stretching modes
of silicate species. Very weak absorptions around 2100
1900 cm1 can be assigned to the corresponding overtones (inset
in Fig. 4). OH consumption during this process is also evident as
a decrease of absorption in the 37003400 cm1 region and the
disappearing of the high frequency components at 3780 and
3730 cm1 (inset in Fig. 4). The spectrum shows the partial decrease of the bands due to HMCTS and the formation of the bands
of methane already at 473 K, with further increase at 673 K.
Methyl fragments are still adsorbed at the surface even following outgassing at 673 K, as revealed by weak and sharp bands at
2974, 2915, 1270 and 1400 cm1. These bands, although slightly
shifted towards higher frequencies, are completely consistent with
the bands we previously assigned to the cyclic siloxane structure,
thus pointing out a strong interaction with the surface of some
residual unreacted molecules, even following high temperature
treatment. The band which is sensitive to the siloxane structure
(i.e. SiOSi stretching at 1025 cm1) is masked by the strong silica
SiOSi absorptions grown during this experiment.
The skeletal IR spectrum of the spent adsorbent is reported in
Supporting information 3 and shows again the formation of a
strong band at 1055 cm1, with a shoulder at 1205 cm1, completely consistent with spectrum Fig. 2c. The position of the main
band is denitely lower than that observed for the different silica
forms (1085 cm1 for coexite, 1086 cm1 for a-quartz, 1096 cm1
for a-cristobalite, 1100 cm1 for amorphous silica, 1108 cm1 for
a-tridimite, Busca and Resini, 2000). On the other hand a component is also observed near 807 cm1, which can be attributed to
a SiOSi symmetric stretching mode. This indicates that, on alumina, silicoaluminate-like species or polysilicate ions are formed.
Interestingly, the transmission of the sample seems to increase in
the region 9001000 cm1, which could correspond to a decrease
of the amount of tetrahedral Al ions in the structure, possibly associated to the formation of a spinel-type silicoaluminate phase
(Busca and Resini, 2000). A sharp band is also evident at
1280 cm1, showing again the persistence of species still containing the methyl group.
These data conrm the strong reactivity of the alumina surface
with respect to HMCTS, allowing its decomposition at temperatures above 473 K.
The analysis of the spectra of the silica disk (Fig. 5) shows that
at 473 K HMTCS adsorbs at the surface, in part in a molecular form.

In fact, IR bands are detectable at frequencies very close to those of

the liquid compound. Two CH stretching bands and the corresponding deformation bands can be clearly seen at 2970, 2915,
1450 and 1410 cm1. The broad peak due to the surface OH groups
of silica, very strong between 3800 and 3200 cm1, strongly lowers
in intensity. Additionally, the sharp peak at 3745 cm1, due to isolated silanol groups SiOH, is the most decreased in intensity,
without a concurrent formation of broad bands. This indicates that
a reaction occurred between HMCTS and surface silanols, more
than a simple H-bonding, giving rise to neutralization of the surface OHs. The conversion of HMTCS over silica was detectable as
its gas phase concentration diminished and methane formation became signicant at 673 K. At the catalyst surface, bands due to silicate species, likely formed by HMTCS conversion, cannot be
observed because they are masked by the strong skeletal absorption of the SiO2 adsorbent itself.
The surface FT-IR spectrum of CaO outgassed at 473 K is also
quite complex (Fig. 6a), due to the presence of hydroxy groups
and carbonate species, whose fundamental vibrations and overtones give rise to strong bands in the region 38003200 cm1, in
the region 16001300 cm1 (that comes to saturation) and around
880 cm1. This is typical of very basic oxides that are in normal
conditions a mixture of carbonates and hydroxides. The corresponding skeletal spectrum (reported in Supporting information
4), recorded on the sample diluted in KBr, shows the OH stretching
of Ca(OH)2 at 3643 cm1, and the bands of CaCO3 at 1410 and
874 cm1. Interaction of HMCTS with the surface at 473 K leads
to the detection of bands due to molecularly adsorbed siloxane
(1264, 1032, 817 cm1 Fig. 6b). Other absorptions of HMCTS are
masked by the strong absorptions of the calcium oxide sample itself. Heating at 573 K (Fig. 6c) causes the appearance of a new, very
strong and complex absorption centered around 950 cm1. The
intensity of this band is increasing at higher temperatures and at
673 K the signal reaches saturation (Fig. 6d), leading to a cut-off
zone in the spectral range between 1000 and 800 cm1. Methane
is detected in the gas phase already at 573 K, its amount rapidly
increasing.
The spectrum recorded after contact with HMCTS at 673 K and
outgassing at the same temperature shows that residual adsorbed
silicon-containing organic species are still detectable, characterized by a very weak absorption at 1270 cm1, assigned to a Si-CH3
deformation mode. Also the skeletal spectrum of the spent catalyst,
recorded in KBr pressed disks (in Supporting information 4), shows
a strong band at 950 cm1, formed after contact with HMCTS. This
band is typical of SiO stretching modes of isolated silicate species, suggesting the formation of bulk calcium silicate (Gadsen,

3.0
880

2970

4,2

Absorbance

3745

1032

d
c

Absorbance

950

2915
1410

817

1264
1795
b

0.8
4000

3500

3000

2500

2000

1500

1000

Wavenumbers (cm-1)
Fig. 5. FT-IR spectra of surface species arising from HMCTS adsorption over
SiO2:SiO2 surface outgassed at 473 K (a), following HMCTS adsorption at room
temperature and heating at 473 K (b). HMCTS gas phase spectrum has been
subtracted.

0,8
2000

a
1800

1600

1400

1200

1000

800

600

Wavenumbers (cm-1)
Fig. 6. FT-IR spectra of CaO outgassed at 473 K (a), and following contact with
HMCTS vapor at 473 K (b), 573 K (c) and 673 K (d).

E. Finocchio et al. / Chemosphere 72 (2008) 16591663

1663

1975). Bulk silicate formation has also been observed, although in

lower amount, during siloxane adsorption in static conditions over
MgO powder surface.
The data arising from these static adsorption experiments,
showing a strong reactivity of calcium oxide towards HMCTS, seem
to contrast those arise from dynamic adsorption experiments
where calcium oxide was found almost inactive. The results discussed above show a different behavior of three different solid oxides towards the adsorption of HMCTS at high temperature.
Alumina shows a strong reactivity allowing the complete removal
of this compound from a synthetic biogas. Spectroscopic data
shows that, while at room temperature the adsorption is molecular, at higher temperature reactive adsorption occurs. Both gas
and surface analyses reveals that the following reaction occurs:

silicized and methane is released. This process ends after covering

the alumina surface with a silica monolayer corresponding to an
adsorption capacity of 0.31 g(HMCTS) g(Al2O3)1. This process could be
useful for cleaning biogases before their use as feed for steam
reforming reactions and high temperature fuel cell application.
On the contrary, silica, which is an excellent adsorbent for siloxanes at room temperature shows an adsorption capacity of 0.76 g
of adsorbed siloxane per gram of silica, looses its adsorption ability
at high temperature, as it is typical of a molecular adsorption
behavior. Basic oxides such as MgO and CaO have strong reactivity
in decomposing siloxanes in the absence of CO2, but loose reactivity when in contact with carbon dioxide because of surface
carbonation.

Appendix A. Supplementary material

CH3 2 SiO


3

6OH 6CH4 3SiO2 3O2

with consumption of surface hydroxy groups, evolution of methane

and silication of the alumina surface. This reaction is even favoured
by the presence of water. The formation of partially decomposed
3
2
fragments such as CH3 SiO3  or CH3 SiO3  as proposed by Chuiko
et al. (1996), may also occur.
Experiments have also been performed with octamethylcyclotetrasiloxane and hexamethyldisiloxane, showing the
same chemistry and a very parallel behavior. Over silica, the same
reaction likely occurs, at least in the static condition in the absence
of water. However, it is evident that in ow reaction experiments
the extent of this reaction is very limited, the behaviour being better explained by a simple molecular adsorption. Over calcium
oxide (as well as over MgO, not shown here) a similar reactive
adsorption occurred in our static experiments performed in the absence of water and of CO2. In this case, bulk Ca (and Mg) silicates
form

CH3 2 SiO3 6OH 3O2 6CH4 3SiO4 4

However, this reaction is not found in the ow reactor experiments performed in the presence of water and CO2. This is likely
due to the competition of carbon dioxide that strongly reacts with
the surface and poisons the reactive adsorption sites.
4. Conclusions
The work summarized in the present paper shows that alumina
can be used as an adsorbent for the hot-cleaning of biogas from
siloxanes. At 673 K alumina reacts producing the hydrolysis of
the SiC bond. As a result of this reaction, the alumina surface is

Supplementary data associated with this article can be found, in

the online version, at doi:10.1016/j.chemosphere.2008.05.032.
References
Bogatyrov,
V.M.,
Borysenko,
M.V.,
2000.
Thermal
destruction
of
polydimethylsiloxane on a phosphorous-containing silica surface. J. Therm.
Anal. Calorim. 62, 335344.
Busca, G., Lorenzelli, V., Ramis, G., Willey, R.J., 1993. Surface sites on spinel-type and
corundum-type metal oxide powders. Langmuir 9, 14921499.
Busca, G., Resini, C., 2000. Vibrational spectroscopy for the analysis of geological and
inorganic materials. In: Meyers, R.A. (Ed.), Encyclopedia of Analytical Chemistry.
Wiley and Sons Ltd., Chichester, pp. 1098411020.
Camino, G., Lomakin, S.M., Lazzari, M., 2001. Polydimethylsiloxane thermal
degradation. Part 1. Kinetics aspects. Polymer 42, 23952402.
Chuiko, A.A., Guba, G.Ya., Pokrovskii, V.A., Teretz, M.I., 1996. Organosiloxane and
monoethanolamine transformations on fumed silica and alumina-silica
surfaces. Colloid. Surface A 106, 8993.
Dewil, R., Appels, L., Baeyens, J., 2006. Energy use of biogas hampered by the
presence of siloxanes. Energ. Convers. Manage. 47, 17111722.
Gadsen, J.A., 1975. Infrared Spectra of Minerals and Related Inorganic Compounds.
Butterworths, New York.
Handke, M., Jastrzebski, W., 2004. Vibrational spectroscopy of the ring structures in
silicates and siloxanes. J. Mol. Struct. 704, 6369.
Higgins, V.L., 2006. Siloxane removal process. United States Patent 20060225571,
WO/2006/104801.
Lee, S.-H., Cho, W., Song, T.Y., Kim, H., Lee, Y.C., Baek, Y., 2001. Removal process for
octamethylcyclotetrasiloxane from biogas in sewage treatment plant. J. Ind.
Eng. Chem. 7, 276280.
NIH, 2006. Household Products Database. http://hpd.nlm.nih.gov/index.htm.
Orio, A., Corella, C., Narvaez, I., 1997. Performance of different dolomites on hot raw
gas cleaning from biomass gasication with air. Ind. Eng. Chem. Res. 36, 3800
3808.
Schweigkoer, M., Niessner, R., 2001. Removal of siloxanes in biogases. J. Hazard.
Mater. B83, 183196.
Wheless, E., Pierce, J., 2004. Siloxanes in Landll and Digester Gas Update. http://
www.scsengineers.com/Papers/Pierce_2004Siloxanes_Update_Paper.pdf.