Desalination 200 (2006) 234235

Presented at EUROMEMBRANE 2006, 2428 September 2006, Giardini Naxos, Italy.

0011-9164/06/$ See front matter 2006 Elsevier B.V. All rights reserved.
Siloxane removal with gas permeation membranes
Marc Ajhar*, Thomas Melin
Institut fr Verfahrenstechnik, RWTH Aachen University, Turmstrae 46, 52056 Aachen, Germany
Tel. +49 (0)241 80 95 472; Fax +49 (0)241 80 92 252; email: ajhar@ivt.rwth-aachen.de
Received 21 October 2005; accepted 2 March 2006
1. Introduction
The digestion of organic material in waste
disposal sites, sewage treatment plants or fer-
menters leads to the production of low calorific
value fuel gas, which can be used in combustion
processes to generate electricity. However, cor-
rosion and deposits on machinery and plant
components, on the one hand, and relatively
high emissions of particles and pollutant exhaust
gases, on the other hand, make a preliminary gas
cleaning step necessary. As one of many trace
components fuel gases might include, silicon-
containing compounds, so-called siloxanes,
have been identified as a serious problem. Upon
combustion, silicates and micro-crystalline
quartz are produced, leading to abrasion and
deposits on the combustion unit, promoting
mechanical wear and increased gas pollutant
emissions.
Plant engineers have reacted to this problem
by conventional methods used in gas-cleaning
technology, including siloxane removal by
condensation, adsorption or gas scrubbing. All
have their process-specific advantages and
inconveniences. The IVT is studying gas sepa-
ration membranes in combination with these
conventional methods as a possible process to
reduce siloxane and other trace component
concentrations more effectively.
2. Simulating GP-membrane-based
hybrid processes
In order to evaluate complete membrane-based
hybrid gas purification process schemes in terms
of energy consumption (vacuum pumps, compres-
sors, coolers) and needed material flow (adsorbers,
washing agents, etc.), simulations have been con-
ducted using IVT user-added subroutines for
AspenPlus
TM
(Aspen Technology Inc., MA, USA).
The gas permeation membranes focused
upon were of rubbery type. Already industrially
used in solvent and gasoline vapour recovery
from discharged air, solubility selective PDMS
(polydimethylsiloxane) seems a possible candi-
date for separating non-permanent gas compo-
nents of fuel gases such as siloxanes. Not only
siloxanes but also other problematic organic
trace substances such as BTEX or halogenated
hydrocarbons show relatively high permeability
in PDMS membranes with selectivities ranging
from 20 to 70 over nitrogen [1]. Another major
advantage of membrane use in general, is high
water permeability. As gas purification in bio-
gas, sewage or landfill gas applications gener-
ally implies preliminary gas drying (e.g. in order *Corresponding author.
doi:10.1016/j.desal.2006.03.308
M. Ajhar, T. Melin / Desalination 200 (2006) 234235 235
to prevent water from blocking adsorber sites on
activated carbon), PDMS membranes showing
high water intrinsic permeances of about 40,000
Barrer [2] serve as an ideal dehumidifier.
3. Membrane screening
In order to evaluate the applicability of the
generalised simulations conducted, siloxane
permeabilities of common rubbery type mem-
brane materials will have to be determined
experimentally.
As siloxanes are a wide range of molecules,
membrane screening tests are limited to a collec-
tion of common representatives in low calorific
value fuel gas, i.e. cyclic D3, D4, D5, siloxanes,
and the linear molecules L2, L3, L4. Similar to
prior work on siloxane analytics by Schweigk-
ofler and Niessner [3], the IVT has devised an
analytical method used for the quantification of
these siloxanes in carrier gas: the siloxane-loaded
gas stream is drawn through a series of partially
cooled washing bottles containing organic
solvent, in which trace components absorb.
The loaded solvent can then be analysed by
means of gas chromatography/mass spectrometry
(GC-MS). Membrane screening tests for siloxane
selectivity over nitrogen have been performed
employing the above described analytics to mea-
sure siloxane concentrations on every side of the
membrane. Volume flow meters yield the abso-
lute amounts of siloxanes permeating through the
membrane at given pressure and temperature
conditions, with which the permeability of
the tested siloxanes are calculated.
First results have already been found for the
selectivity of D4-octamethylcyclotetrasiloxane
over nitrogen in PDMS. Further tests are still
being conducted, especially to verify first
results.
4. Conclusions
The IVT has identified gas permeation as a
potential new method for the removal of com-
mon siloxanes in fuel gases such as sewage,
landfill or biogas and is currently testing
different membrane materials for siloxane per-
meability. The applicability of gas permeation
hybrid processes for the removal of siloxanes
and other organic trace components, but also
for gas dehydration, is studied with the help of
AspenPlus

simulations of complete gas purifi-

cation process schemes. If promising results
are found, a pilot plant for sewage gas purifica-
tion including membrane modules will likely
be built.
References
[1] K. Ohlrogge, T. Wind and T. Brinkmann, Mem-
brane Based Hybrid Systems to Treat Organic
Vapour Loaded Gas Streams, 6th Italian Con-
ference on Chemical and Process Engineering,
Pisa, 2003.
[2] S.J. Metz, W.J.C. van de Ven, J. Potreck, M.H.V.
Mulder and M. Wesseling, Transport of water
vapour and inert gas mixtures through highly
selective and highly permeable polymer mem-
branes, J. Membr. Sci., 251 (2003) 2941.
[3] M. Schweigkofler and R. Niessner, Determina-
tion of siloxanes and VOC in landfill gas and
sewage gas by canister sampling and GC-MS/
AES analysis, Environ. Sci. Technol., 33(20)
(1999) 36803685.