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GIFC 2010


Siloxane adsorption by solids in biogas purification

E.Finocchioa, T.Montanaria, G.Garutib, C.Pistarinoc, G.Buscaa

Dept. of Chemical and Process Engineering, University of Genova, P.le Kennedy 1, I-16129 Genova, Italy
Acqua e Sole Srl, Milano, Italy
Ecodeco Srl, Cassinazza di Baselica, I-27010 Giussago (PV) Italy
Biogases are methane-rich gases produced by anaerobic digestion of waste materials, such as waste
water treatment plants, animal sewage, landfill wastes. These gases can find several energy applications: they
can be burnt to produce heat, used as fuels for biogas fuel cell, for spark ignition engines or gas turbine to
recover electric power. A possible application to produce hydrogen or syngas by steam reforming of methane
can also be envisaged. Whatever the application, the use of biogas is hindered by the presence of a wide amount
of impurities, detected in traces or significant amount: amongst them, linear and cyclic low molecular weight
siloxanes are commonly found, likely arising from polymethylsiloxanes widely used in the formulation of
household, personal care and other industrial products or formed as stable thermal degradation products of
polydimethylsiloxane, a member of the silicones family1. These compounds are converted upon combustion into
quartz and silicate powders, which damage the inner surfaces of the combustion engines and depose at the
surface of fuel cell electrodes and combustion or steam reforming catalysts, deactivating them. Their removal
can be achieved by condensation, gas liquid extraction or by solid phase adsorption over activated carbons
(method of choice), resins, molecular sieves and silica gel.
In the frame of an investigation on the best procedures for biogas purification, we studied the adsorption
and thermal decomposition of hexamethylcyclotrisiloxane (HMCTS, one of the most abundant siloxanes in
landfill biogases) from wet synthetic biogases (CO2-CH4 mixture), at room temperature and in the range 473
673 K over the surface of basic (CaO, MgO) and acidic oxides (zeolites, Al2O3, SiO2), and several commercial
active carbons (AC)2,3. The adsorption mode of this molecule has been investigated both in a fixed bed
continuous adsorber as well as by IR spectroscopy in static conditions. Although at room temperature pure ACs
are better siloxane sorbent than inorganic solids such as silica and zeolites, mineralization of silicon atoms
occurring at high temperature over inorganic solids can be proposed as an alternative approach to gas
purification. In particular, alumina allows the complete removal of HMCTS from synthetic biogases at 673 K. A
reactive adsorption occurs with OH groups consumption, surface silication and release of methane until 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.
Acknowledgements. This work has been supported by MIUR-PNR-FIRB ("Risparmio energetico con valorizzazione dei Bacini
Secondari di Energia quale fonte energetica distribuita" - Unit "Natural Energy from Waste (NEW)").

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