International Journal of Greenhouse Gas Control 53 (2016) 56–64

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International Journal of Greenhouse Gas Control

journal homepage: www.elsevier.com/locate/ijggc

Pilot scale separation of CO2 from power plant flue gases by

membrane technology
Jan Pohlmann a , Martin Bram b , Kai Wilkner b , Torsten Brinkmann a,∗
a
Helmholtz-Zentrum Geesthacht, Institute of Polymer Research, Max-Planck-Straße 1, D-21502 Geesthacht, Germany
b
Forschungszentrum Jülich, Institute of Energy and Climate Research, D-52425 Jülich, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Removing carbon dioxide from power plant flue gases is an increasingly important separation task to
Received 15 April 2016 limit the amount of greenhouse gases emitted to the atmosphere. In contrast to competing processes,
Received in revised form 19 July 2016 membrane technology requires less time to react to changing feed conditions. Hence it is ideally suited
Accepted 21 July 2016
to operate efficiently even under partial load and at irregular intervals. I.e. the scenarios conventional
power plants are facing today due to the increasing amount of renewable energy supplied to the power
Keywords:
grid.
CO2 removal
In this work the results of several experiments using a membrane gas separation pilot plant connected
Polymer membranes
Pilot plant operation
to a hard coal fired power plant are presented. Feed flowrate, temperature, dew point and composition
Membrane stability as well as permeate pressure were varied during the experiments. The influences of these parameters on
CCS module performance, as well as the transition between different operating conditions were investigated.
During these experiments the plant was frequently operated with ambient air during downtimes of the
power plant. This allowed for a start-up and shut-down procedure to be developed, which is important
to ensure the stability of the membrane. In order to gauge the stability of the process the experimental
data is compared to a previously validated model.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction et al., 2014). Facilitated transport membranes were used within

The separation of CO2 from power plant flue gases has become
an increasingly active research field in the last years, particularly
in the area of membrane technology thus highlighting the fact that
membranes can be a less energy intensive unit operation (Baker,
2012). Also membrane processes adapt almost instantaneously to
changing process conditions.
Hence numerous investigations dealt with the development
of membrane materials for the separation of CO2 from nitro-
gen. Reviews on this subject were published by Du et al. (2012)
and specifically focussed on poly(ethylene oxide) containing block
copolymers use are discussed by Liu et al. (2013). However, only
few of the proposed CO2 /N2 selective polymers were used to
produce membranes that could be employed on a technical, i.e.
module, scale. Examples are the MTR Polaris® membranes which
are mounted into spiral wound membrane modules and employed
in several pilot plant applications, including the separation of CO2
from flue gas and hydrogen (Merkel et al., 2010; Merkel, 2012; Lin
∗ Corresponding author.
E-mail address: torsten.brinkmann@hzg.de (T. Brinkmann).
the EU project NanoGlowa to separate CO2 from flue gas of coal
fired power plants (Sandru et al., 2013). The approach was recently
extended to cement factories (He et al., 2015). The use of Polyimide
membranes in hollow fibre configuration, as already employed in
refinery applications for e.g. H2 separation, was investigated by Air
Liquide in combination with a cryogenic process within the scope of
a DoE funded project (Hasse et al., 2014; DoE NETL Fact Sheet, 2011).
Another facilitated transport approach was investigated by Scholes
et al. (2015). They employed a commercial Dow nano filtration
membrane module in spiral wound configuration. It was shown
that the membrane material possessed facilitated transport func-
tionality for humidified CO2 /N2 mixtures. The 7.5 m2 membrane
module was investigated in a purpose built pilot plant connected
to a lignite coal fired power plant in Australia, where also a com-
mercial Air Products PRISM® membrane module in hollow fibre
configuration was investigated. The reported operating times were
rather short.
Long operating times were achieved using the PolyActiveTM thin
film composite membrane also used in this study. The membrane
was mounted into an envelope type module and installed into a
pilot plant used to provide a CO2 enriched permeate stream for the

http://dx.doi.org/10.1016/j.ijggc.2016.07.033
1750-5836/© 2016 Elsevier Ltd. All rights reserved.
 J. Pohlmann et al. / International Journal of Greenhouse Gas Control 53 (2016) 56–64 57

the ordinary differential equations given in Brinkmann et al. (2013)

Nomenclature became partial differential equations capable of describing the spa-
tial and temporal distribution of intensive process variables along
m2 the membrane surface. The following dynamic material and energy
a Specific area
m3 balances resulted for the feed side:
kmol
c Molar concentration
m3 
kW ∂cR,i ∂ṅR,i
ė" Energy flux
m2 εR · + + aR · ṅM,i = 0 (1)
kJ ∂t ∂z
H̃ Molar enthalpy kmol    
Li,N Permeance of component i at standard conditions ∂ 
nc
∂ 
nc

m3 εR · H̃R · cR,i + H̃R · ṅR,i 

+ aR · ėM =0 (2)
m2 ·h·bar ∂t ∂z
kmol i=1 i=1
ṅ" Molar flux
m2 ·s
t Time s or h where the subscript R indicates the retentate side, ␧R is the spacer
m3 porosity, cR,i is the molar concentration of component i, t is the time,
V̇N Volumetric flowrate at standard conditions h
yi Mole fraction of component i – ṅR,i is the molar flux of component i parallel to the membrane sur-
z Axial co-ordinate m face, i.e. from feed to retentate, z the spatial co-ordinate parallel
to the membrane surface, aR the specific membrane surface, i.e.
Greek membrane area per retentate side membrane module volume and
˛i,j Selectivity of component i vs. j – ṅM,i is the flux of component i through the membrane. The flux
ε Porosity – is determined by the permeation characteristics of the multilayer
ϑ Temperature ◦ C composite membrane, i.e. the permeances given in Table 2 and
the driving force, i.e. the differences of the component fugacities
Subscript between feed and permeate sides of the module. Further detri-
i, j Component mental effects as concentration polarisation, feed and permeate
M Membrane side pressure drops and, when applicable, influences due to real
N Standard conditions gas behavior are discussed in detail in Brinkmann et al. (2013).
nc Number of components Additional variables in the energy balance are the enthalpy H̃R
P Permeate and the energy flux ėM  across the membrane. The latter consists
R Retentate of conductive and convective, i.e. enthalpy of the permeation flux,
F Feed contributions. The membrane module was considered to operate
D Dewpoint adiabatically, which is a fair assumption since the pilot plant is
STP Standard temperature (273.15 K) and pressure housed inside a container. However, future work will relax this
(1.01325 bar) assumption and aim at the consideration of heat exchange with
tot Total the environment.
As initial condition for the dynamic simulations of the pilot
plant performance, the membrane module was considered to
cultivation of algae. The feed gas to the membrane unit was the flue be filled with humidified air with a small content of CO2
gas of a natural gas fired heating system Wolff et al. (2015). (yR,CO2 (t = 0) = 0.0031) at 35 ◦ C.
In order to further establish gas permeation as a viable option The boundary conditions of the model consist of the feed side
for CO2 separation in the industrial sector a pilot plant has been conditions i.e. volumetric flow rate at standard conditions, pres-
built within the scope of the METPORE II project financed by the sure, temperature and composition as well as the permeate side
German Federal Ministry for Economic Affairs and Energy. This pressure. In case the experimental data was changing as a function
pilot plant was operated in a side stream of the hard coal fired of time, it was interpolated with respect to time using polynomic
power plant Rheinhafen-Dampfkraftwerk RDK-7 owned by EnBW functions. Additionally, permeation model parameters, determined
Energie Baden-Württemberg AG. The experimental data and results solely from single gas experiments, were supplied. The model used
reported in this paper cover the long term continuous operation for the thin film composite membranes employing PolyActiveTM as
of the pilot plant. Tests, where the influences of the different the CO2 selective separation layer was the free volume model (Fang
process conditions were assessed, have been reported elsewhere et al., 1975). The model allows for the consideration of a pressure
(Pohlmann and Brinkmann, 2014). The process model used to eval- dependent contribution to permeance. However, the experimental
uate the experimental data will be described briefly in this paper, investigations showed that at the typical operating conditions of
a more detailed description can be found in Brinkmann et al. post combustion processes pressure dependence was of negligible
(2013). The model in combination with pilot plant results was also influence (Brinkmann et al., 2015b). Details on the application of
employed to evaluate the influence of pressure drops of different the model to PolyActiveTM thin film composite membranes can be
membrane module types on process performance and economics found in Brinkmann et al. (2013) and Brinkmann et al. (2015b).
(Brinkmann et al., 2015a).
3. Materials and methods
2. Theory
3.1. Flue gas conditions
The simulation model used to evaluate the experimental data
given in this paper has previously been described in Brinkmann For conducting the membrane testing at the power plant, the
et al. (2013). It was implemented in the equation oriented process fraction of the flue gas to be supplied to the pilot plant is split off
simulator Aspen Custom Modeler® (Aspen Technology, 2015). The after the usual flue gas cleaning steps i.e. ash removal, catalytic
model used in this publication is based on this model but has been reduction and desulfurization. These steps ensure a temperature
extended to handle dynamic scenarios. The extension consisted of that is low enough for post combustion capture processes. At this
introducing time dependency of concentration and enthalpy into point the flue gas has the conditions summarized in Table 1. As can
the differential material and energy balances, respectively. Hence, be seen the flue gas still contains some additional acid gases as NOX
58 J. Pohlmann et al. / International Journal of Greenhouse Gas Control 53 (2016) 56–64

Table 1 the blower C1 is protected by a combined condensate and dust

Flue gas composition. Relative units are on molar basis, volumetric units are under
removal unit which partially removes acidic condensates as well
standard conditions (273.15 K, 1.01325 bar). The flue gas temperature after the
desulfurization plant is reported to be 70 ◦ C (EnBW, 2011). as particulate matter entrained within the stream. After the flue
gas has been compressed, it passes a heat exchanger (H1) which
Component Quantity Unit
removes the heat of compression as well as the majority of the
CO2 14.5 % water vapour load. In order to avoid condensation upstream of the
O2 6.5 % cooler/condenser the gas is re-heated by an electrical heater (H2)
SO2 50–100 ppm
above the water vapour dew point. In order to avoid deposition
NO 76–91 ppm
CO 4–16 ppm of remaining particles on the membrane surface, the gas is passed
H2 O 14.0 % through a filter (F2). After these steps the gas stream is split into
N2 rest % two separate streams. The first stream enters a membrane mod-
Dust 5–20 mg/m3 (STP)
ule (M1.2) with a membrane area of up to 12.5 m2 and the second
stream is fed to a module containing a membrane area of 1 m2 . The
data presented in this paper will only cover the experiments done
and SO2 next to CO2 . Furthermore, gypsum particles introduced
with the larger module. Hence, the parallel linework for the 1 m2
during the desulfurization step are present as particulate matter.
module is not shown in Fig. 1. The driving force for the separation
These components in conjunction with the high water vapour load
process is applied by a liquid ring vacuum pump (P1) with water as
can lead to various problems if not addressed correctly, as will be
the service liquid. Therefore the pump also acts as a condenser for
described in the experimental procedure section of this paper.
the permeating water vapour. After the gas phase has been sepa-
rated from the service liquid (separator B1) the permeate stream is
3.2. Pilot plant mixed with the retentate stream and released to the atmosphere.
Because SO2 and NOX readily permeate the membrane and also
A simplified flow sheet of the pilot plant used in the experiments dissolve in water, a fraction of the service liquid has to be replaced
is shown in Fig. 1. After the aforementioned flue gas cleaning steps, constantly by a makeup stream of fresh water in order to keep the
a small fraction of the flue gas is drawn from the exhaust pipe lead- pH-Value in the service liquid circuit at an acceptable level.
ing to the stack by a side channel blower (C1). On the suction side,

Table 2
Permeances and selectivities of the PolyActiveTM membranes used at 20 ◦ C, Permeances are at standard conditions.

Membrane Batch LN2 LO2 LCO2 ␣O2/N2 ␣CO2/N2

# m3 (STP)/m2 /h/bar m3 (STP)/m2 /h/bar m3 (STP)/m2 /h/bar – –

1 0.066 0.174 2.870 2.64 43.48
2 0.047 0.127 2.794 2.72 59.70
3 0.051 0.136 3.068 2.68 60.27

Fig. 1. Simplified flow sheet of the pilot plant used in the experiments.
 J. Pohlmann et al. / International Journal of Greenhouse Gas Control 53 (2016) 56–64
Fig. 2. Schematic representation of the cross sectional structure of the multilayer
composite membrane.
The composition of the flue gas was measured with a non-
dispersive infrared spectrometer (URAS ABB) in case of CO2 , a
paramagnetic sensor for O2 (Magnos ABB) and a piezo based sensor
for H2 O (Vaisale Humicap 318). Samples were taken from the feed,
retentate and permeate streams. In case of the permeate stream the
samples were taken from the vacuum side of the module as well
as after re-compression by the vacuum pump. All piping leading
to the analysis system were heated to 80 ◦ C in order to avoid con-
densation. The sample lines are connected to a manifold which was
used to connect the sample lines to the analysis system in a cyclic
manner.
The unit is equipped with further instruments to continu-
ously measure, record and control temperatures, pressures and
flowrates. The instrumentation used for material balancing, evalu-
ation of separation efficiency and control purposes is indicated in
Fig. 1. The two temperature controllers (TIC) were used to set the
outlet temperatures of H1 and H2. The flowrate controller (FIC) acts
on the frequency converter of the blower motor and hence controls
the feed flowrate whilst the pressure transducer (PIC) in the per-
meate line acts on the permeate side pressure control valve. All
the measurement and control devices were connected to a com-
puter based data acquisition and control system (Siemens S7-300)
allowing operation of the unit without personnel being present.
3.3. Membrane
The membrane used in the experiments was a multilayer thin
film composite membrane, with an active separation layer made
from PolyActiveTM (Metz et al., 2005; Car et al., 2008; Yave et al.,
2010). The support structure consists of a non-woven support
with a thickness of app. 100 ␮m made from polyester (PES), and
a porous support layer of polyacrylonitrile (PAN) with a thick-
ness of approx. 50 ␮m and an average pore size of 30 nm on the
membrane surface. The porous support structure is manufactured
by the phase inversion process (Scharnagl and Buschatz, 2001).
This substructure is then subsequently coated with a highly per-
meable polydimethylsiloxane (PDMS) gutter layer (100–120 nm)
which provides drainage to the gas permeating through the sepa-
ration layer, i.e. making the porous support structure more readily
accessible for the permeating gases, and preventing the intrusion
of the active separation layer into the porous support (Baker, 2012).
On top of the gutter layer, the separation layer of PolyActiveTM is
applied. PolyActiveTM is a block-co-polymer consisting of alternat-
ing soft blocks of polyethylene oxide (PEO, molar mass 1500 g/mol)
and rigid blocks of poly-butylene terephthalate (PBT) (Car et al.,
2008). The separation layer has a thickness of app. 70 nm. The final
layer is another PDMS layer of app. 150 nm thickness used to seal
any defects in the active separation layer and to provide a pro-
tection against mechanical damages e.g. abrasion during module
assembly and operation. Further details can be found in (Yave et al.,
2010). A schematic representation of the membrane is shown in
Fig. 2.
This multilayer composite membrane is manufactured in more
than 100 m2 scale in batches consisting of a roll of 250 m in length
and 0.7 m in width. As has previously been shown in Brinkmann
59
Fig. 3. Schematic representation of the 12.5 m2 membrane module.
et al. (2015b) this membrane is manufactured reproducibly. The
reproducible production was confirmed by measuring N2 and O2
permeances of the produced membrane in regular intervals along
the production length. Since the required N2 permeance and the
O2 /N2 selectivities are known, these measurements served for
quality control since they are sufficient to prove the membrane’s
integrity and performance. The permeances for N2 , O2 and CO2 as
well as the selectivities at 20 ◦ C for the membrane batches used
in this study are given in Table 2. It is apparent that membrane
batch 1 showed a lower CO2 /N2 selectivity compared to the other
two batches investigated. However, within the batch the selectivity
was uniform and considered sufficient. Hence, the membrane was
used in the pilot plant investigations. More detailed information
on the temperature and pressure dependency of the permeances
of PolyActiveTM multilayer thin film composite membranes as well
as the required permeation model parameters can be found in
Brinkmann et al. (2013) and Brinkmann et al. (2015b). The per-
meance of water vapour was assumed to be 10–fold higher than
that of CO2 , a value that was confirmed by measurements done for
a different membrane batch (Brinkmann et al., 2015b).
3.4. Membrane module
The membrane modules employed in this study were envelope
type modules (Ohlrogge et al., 2010; Brinkmann et al., 2013, 2015b).
A schematic representation of the membrane module is depicted
in Fig. 3. The membrane envelopes are stacked on a central per-
meate tube which also serves as a tension rod ensuring the seal
between retentate and permeate sides of the module by means of
rubber O-rings placed between envelopes, baffle plates as well as
feed and retentate flanges. The stack of envelopes is subdivided
into compartments by baffle plates allowing tight control over the
flow regime inside each compartment, which is used to minimise
the effect of concentration polarisation. The individual membrane
envelopes are separated by spacer material which prevents the
envelopes from sticking together and also increases the turbulence
on the feed side of the membrane.
Two sets of data will be discussed in following sections. For each
set, a different membrane module was employed. For the first set
the module was equipped with 82 membrane envelopes manufac-
tured from batches 1 and 2 (Table 2) housed in 4 compartments
with a total membrane area of 9.8 m2 . Furthermore, the majority
of the envelopes of the compartments 1–3 were envelopes that
prior to being installed in this module were previously installed in
a different module which was operated in a different pilot plant for
biogas upgrading in Albersdorf, Germany (Brinkmann et al., 2015b).
The possibility of membrane envelope reuse clearly demonstrates
the robustness of the developed multilayer thin film composite
membrane.
The second module was divided into five compartments with
21 envelopes each, resulting in a membrane area of 12.5 m2 . The
membrane material used for this module was of batch 3 (Table 2).
60 J. Pohlmann et al. / International Journal of Greenhouse Gas Control 53 (2016) 56–64

3.5. Process simulation Table 3

Constant feed and permeate side conditions of experiment 1. Volumetric flow rate
is given at standard conditions; the pressures are given as absolute pressures.
The model describing the membrane module introduced in Sec-
tion 2 was employed to set up a dynamic simulation flowsheet Feed flow rate m3 (STP)/h 50.01
Feed pressure bar 1.132
representing the pilot plant shown in Fig. 1. For the implementa-
Permeate pressure bar 0.100
tion of the model, the equation oriented, dynamic process simulator
Aspen Custom Modeler (Aspen Technology, 2015) was used. The
module compartments were represented by sub-models that allow
the input of different permeation parameters for individual com-
partments. Hence it was possible to represent the first module
equipped with membrane material of different batches. The flow-
sheet representation of the process shown in Fig. 1 was employed to
dynamically simulate the process performance using experimental,
time dependent boundary conditions. Deviations between experi-
mental results and simulation predictions help to identify possible
problems as e.g. a drop in process performance due to membrane
damage. Conversely, a close fit of simulation predictions to exper-
imental results indicates proper operation of the pilot plant and
provides further validation of the accuracy of the membrane mod-
ule model.

4. Results

4.1. Requirements for long term operation of the power plant

As mentioned earlier, flue gas pre-treatment is an important

aspect of post combustion CO2 separation. The flue gas taken down-
stream of the usual cleaning steps still contains residual SO2 and
NOX as well as particulate matter entrained in the flue gas stream.
Combined with the high water vapour load this can lead to the
formation of acidic condensates in various parts of the pilot plant
as well as on the membrane surface. Furthermore, the particulate
matter can lead to the failure of the blower if it is not treated care-
fully.
The first step of flue gas pre-treatment is a combined condensate
a dust removal unit (F1 in Fig. 1). This step is vital in ensuring that
the blower (C1) of the pilot plant can operate for extended periods
of time. During the start-up, the piping leading to the pilot plant is
still cold so most of the water in the flue gas will condense until the
piping is sufficiently warm. In combination with the acid forming
components this condensate has a pH-value of 1.5–2.0 (cf. Fig. 1).
Additionally, the acids are also oxidizing compounds which lead
to corrosion inside the blower since it is made from dye cast alu-
minium. The forming oxide layer can be easily removed from the
surface of the wetted parts of the blower. These particles can pass
into the small gap between the rotating and stationary parts of the
blower, causing the blower to fail. The same is true for the gypsum
particles entrained in the flue gas. Another aspect to consider is the
temperature of the blower itself. During the start-up of the pilot
plant the blower is still cold and as such condensation inside the
blower has to be taken into account. This problem was addressed
by operating the pilot plant with ambient air for an hour to warm
up the blower.
The second step of the pre-treatment consists of a
cooler/condenser (H1) after the blower. Here, the heat of compres-
sion is removed and the gas temperature is lowered below that of
the feed gas, i.e. 25–35 ◦ C. Hence, the majority of the water vapour
is also separated. The condensation step is immediately followed
by an electrical heater (H2) to heat the gas above the water vapour
dew point. Gas stream overheating ensures that no condensates
can form on the membrane surface and inside the filters. Since
the active separation layer of the membrane is made in part of
a polymer containing a polyether, the acidic condensates can
damage the membrane material, since ethers readily hydrolyse
under acidic conditions.
Fig. 4. Time dependent variation of feed temperature and CO2 mole fraction, 1st
experiment. Dashed lines show polynomic fits for simulation.
Another important aspect to be considered is the shutdown pro-
cedure. This is especially important since large scale power plants
are increasingly operated in flexible manner in order to account
for reduced energy demand and the preferential supply of renew-
able energy into the grid. Other shut-down reasons are scheduled
maintenance intervals and emergency situations. The pilot plant is
operated above ambient temperature and hence the water vapour
dew point is also above ambient temperature. Thus, the plant
cannot be shut-down immediately, because the water vapour con-
tained in the flue gas would condense in the pipes as well as in the
membrane module. Therefore the pilot plant has to be purged with
ambient air in order to replace the residual flue gas.
4.2. Demonstration of CO2 separation from the flue gas
The experiments in this paper consist of two sets of data that
will be described in the following sections. Experiment 1 was con-
ducted in order to proof the pilot plant concept and check on its
operational functionality. Furthermore, it served to provide data for
additional validation of the simulation model. The results described
in Sections 4.1 and 4.2.1 formed the basis for the long term exper-
iment described in Section 4.2.2. This experiment provided proof
of the large potential of polymeric membrane technology for CO2
separation from power plant flue gases.
4.2.1. Experiment 1: proof of pilot plant and simulation concept
The constant feed side conditions and constant permeate pres-
sure of the first set of data are summarized in Table 3. The feed
side conditions with the largest variations with time were temper-
ature and CO2 mole fraction as depicted in Fig. 4. For the purpose
of inputting this data into the dynamic process simulation, param-
eters were represented by fitting polynomials to individual time
intervals. The temperature fluctuations between app. 15 and 25 h
of operating time are due to opened doors of the pilot plant con-
tainer which caused temperature changes inside the container. The
 J. Pohlmann et al. / International Journal of Greenhouse Gas Control 53 (2016) 56–64
Fig. 5. Permeate flow rate after recompression by the vacuum pump, 1st experi-
ment. The flow rate is given at standard conditions.
Fig. 6. CO2 mole fraction on the permeate side, 1st experiment. The CO2 mole frac-
tion is given on a dry basis.
fluctuations in the feed mole fraction are caused by differing power
plant flue gas compositions and accuracy of the composition mea-
surement.
The experimental data is depicted in Figs. 5–8. As it can be seen
from Figs. 5 and 6 the simulation model describes the permeate side
conditions after recompression by the vacuum pump P1 quite well.
A possible reason for the differences between the simulation and
the experimental values for the CO2 mole fraction on the permeate
side in the first 18 h of the experiment is that the service liquid of
the vacuum pump is not in equilibrium with the permeate gas. In
the beginning of the experiment the service liquid is relatively cold
and therefore has a higher absorption capacity for CO2 . Also the pH-
value of the service liquid in the beginning is higher (neutral) than
in the equilibrium state, which also increases the CO2 solubility.
After an equilibrium state has been reached the model accurately
61
Fig. 7. Retentate flow rate at standard conditions.
Fig. 8. CO2 mole fraction on the retentate side, the mole fraction is given on a dry
basis.
describes the experimental values with a slight overestimation of
the permeate CO2 mole fraction.
Whilst this explanation can account for the changes in CO2
compositions in the permeate, it fails to explain the differences
between measured and simulated permeate flowrate. Fig. 5 shows
the flowrate to be predicted correctly after 18 h. However, before
that the measured flowrate is higher than the simulated one. Was
the increased absorption indeed the only reason for the differences,
the experimental flowrate should also be smaller than the calcu-
lated one. Furthermore, the feed temperature is initially lower and
the CO2 content in the feed gas is decreasing (Fig. 4). Both effects
should cause a decrease of the permeate flowrate, which clearly is
not the case. It certainly can be stated that the pilot plant was not
in an equilibrium state during the first 18 h of operation. Hence it
is difficult to identify the exact reason for the deviations in Fig. 5.
However, the comparison between experiment and simulation
result shows that the module performs as expected under flue gas
conditions after 18 h.
62 J. Pohlmann et al. / International Journal of Greenhouse Gas Control 53 (2016) 56–64

Table 4
Feed and permeate side operating ranges for the 2nd experiment; the pressures are
given as absolute pressures.

Min Max

Feed temperature [◦ C] 20.0 49.1

Feed dewpoint [◦ C] 20.4 35.5
Feed CO2 mole fraction [mol-%] 8.94 13.25
Permeate pressure [bar] 0.050 0.300

Fig. 9. Values of the individual terms of the differential material balance Eq. (1) as
a function of time.

On the retentate side of the module the CO2 mole fraction is

slightly underestimated by the model, whereas the flowrate is rep-
resented accurately once the whole system is in an equilibrium
state (Figs. 7 and 8). The small deviations of the simulated results
and the experimental data can probably be attributed to the small
size of membrane area (2.64 cm2 ) used to determine the perme-
ation model parameters of the membrane material compared to
Fig. 10. CO2 mole fraction on the permeate side, 2nd experiment. The CO2 mole
the membrane area installed in the module.
fraction is given on a dry basis.
In order to gauge the rate at which the process adapts to changes
in the feed side conditions, the individual terms of the differen-
tial CO2 material balance were examined (Eq. (1)). The three terms
describe the amount of CO2 permeating through the membrane,
the change of CO2 concentration with time at a specific location
and the change in membrane parallel molar flux of CO2 . The val-
ues of material balance PDE terms (cf. Eq. (1)) at the exit of the
second compartment (cf. Fig. 3) on the retentate side of the mod-
ule are depicted in Fig. 9. As can be seen from Fig. 9, a change in
the term describing the spatial flux distribution on the retentate
side instantly affects the amount of CO2 permeating the membrane
without affecting the derivative with respect to time. If the model
of the membrane module was to show any transient behaviour, one
would expect that a change in CO2 concentration on the high pres-
sure side would affect the holdup, i.e. the first term of Eq. (1), and
hence contribute to the permeation term of Eq. (1). Since this is not
the case, it can be concluded that the membrane module instanta-
neously reacts to changes in operating conditions with time. This
conclusion is further supported by the small residence time in the
module (between 0.49 and 0.79 s for the reported experiments) and
by the low thickness of the membrane.

4.2.2. Experiment 2: long term operation of the pilot plant

In the second experiment the pilot plant was operated contin-
uously for 740 h (31 days), with a membrane module as described
in the membrane module Section 3.4. During these experiments
the feed temperature, feed dew point and permeate pressure have
been varied. Table 4 gives an overview of the investigated operating
ranges. The feed flowrate was 70 m3 (STP)/h and the feed pressure
was 1.265 bar.
The power plant was not in continuous operation during the
duration of the experiment. This was caused by a fluctuation of the
demand of the electricity grid. In case the power plant block was
shut-down, the membrane unit was operated with ambient air.
Fig. 11. Permeate flowrate after recompression by the vacuum pump, 2nd experi-
ment.
Simulation input data that was varying with time was fitted
to polynomials in a similar manner as for the 1st experiment (cf.
Fig. 4). A comparison of the experimental values with the results of
the simulation model is given in Figs. 10 and 11. A measured zero
CO2 mole fraction in the permeate indicates that the power plant
is not in operation. For the shut-down periods, i.e. operation with
ambient air as feed, a CO2 mole fraction of 0.3% was assumed to be
present in the feed for the dynamic process simulations in order to
 J. Pohlmann et al. / International Journal of Greenhouse Gas Control 53 (2016) 56–64
Table 5
Constant operating conditions for flue gas feed during night hours for the 2nd exper-
iment; volumetric flow rate is given at standard conditions, the pressures are given
as absolute pressures.
Feed flowrate [m3 (STP)/h]
Feed pressure [bar]
Feed temperature [◦ C]
Feed dewpoint [◦ C]
Feed CO2 mole fraction [mol-%]
Permeate pressure [bar]
aid convergence. This led to the non-zero CO2 permeate mole frac-
tion for the simulation result depicted in Fig. 10. The pilot plant was
operated at constant operating conditions during night hours (see
Table 5). Flowrates and compositions measured at these conditions
were used to check whether the membrane module showed differ-
ences in operation performance as a function of time. Comparisons
with the predictions of the simulation model were also employed
to identify decreases in the module’s separation performance.
As for the experiment already discussed, the permeate CO2 mole
fraction is represented well by the simulation model with the pre-
diction accuracy decreasing towards the end of the experiment.
The reason will be explained in conjunction with the discussion
of the measured and simulated permeate flowrates. The results
depicted in Fig. 10, i.e. CO2 concentrations of 50–75 mol-% clearly
demonstrate the excellent suitability of the PolyActiveTM thin film
composite membrane for the separation of CO2 from power plant
flue gases over extended period of time at intermittently chang-
ing operating conditions. To the authors’ knowledge this is one
of the few examples where membranes performed that well in a
real flue gas application. However, further long term pilot plant
experiments are required to gather additional data on membrane
durability. The study of Sandru et al. (2013) showed CO2 concentra-
tions in the permeate which were similar to those reported in the
current study. However, the membrane area of 1.5 m2 and CO2 per-
meance of 0.2–0.6 m3 (STP)/(m2 h bar) were rather low (cf. Table 1).
The modules Scholes et al. (2015) investigated were operated for
only a short period of time and showed separation performances
vastly inferior to that reported in this study. One module showed
a CO2 permeance of 1.35 m3 (STP)/(m2 h bar) and a CO2 /N2 selec-
tivity of 5 whilst the other module showed a CO2 permeance
of 0.081 m3 (STP)/(m2 h bar) and CO2 /N2 selectivity of 7. The data
available from Merkel et al. (2010), Merkel (2012) and Lin et al.
(2014) appear to indicate a separation performance similar to that
described here. However, no information on dynamic, intermittent
operation was given.
The simulated permeate flow rate as well as the simulated reten-
tate mole fraction (Fig. 12) started to deviate from the experimental
values quite significantly after 240 h. This decrease of permeate
flowrate in combination with an increase in retentate CO2 mole
fraction is indicative of a partly deteriorated membrane, i.e. a
membrane with decreased permeance but only slightly affected
selectivity. The latter is illustrated by the still small deviation
between predicted and simulated CO2 mole fraction in the per-
meate (cf. Fig. 10). The most likely explanation can be found in an
emergency shut-down of the pilot plant after 205 h, which resulted
in the plant not being flushed with ambient air. Consequently, con-
densate was formed on the membrane. Due to the contents of SO2 ,
NOX and CO2 in the flue gas, this condensate was potentially acidic.
These acidic conditions are thought to have caused hydrolysis of the
ether groups contained in the poly(ethylene oxide) (PEO) blocks of
the PolyActiveTM blockcopolymer. Since the PEO blocks are respon-
sible for the excellent CO2 separation properties of PolyActiveTM ,
the permeance is expected to decrease with decreasing PEO content
in the membrane.
63
70.0
1.265
35.0
25.0
13.00
0.050
Fig. 12. CO2 mole fraction on the retentate side, 2nd experiment. The CO2 mole
fraction is given on a dry basis.
In order gauge the impact of the emergency shutdown on
the membrane material the simulation model was used to back-
calculate the CO2 permeances from experimental values for the
permeate flowrate and the permeate compositions. The operating
points were those given in Table 5. The calculated permeance val-
ues were 4.4 m3 (STD)/(m2 h bar) before and 1.4 m3 (STD)/(m2 h bar)
after the shutdown.
5. Conclusions
One important result of this study is that the experimental data
clearly show that a membrane process like the one presented here
shows no transient behaviour with changing operating conditions.
This allows the membrane separation process to be available on
demand, without the need for lengthy start-up and shut-down pro-
cedures or even the need to operate continuously regardless of flue
gas availability.
Whilst the investigated membrane process shows no transient
behaviour, this does not mean that the process can be operated
entirely without any start-up or shut-down procedure. Care must
be taken to avoid condensation on the membrane surface or in
rotating equipment. This can be achieved by the strategy described
in Section 4:
1 Start-up of the unit with ambient air to ensure all aggregates are
heated up and operating satisfactorily.
2 Flue gas pre-treatment to remove part of the water vapour as
well as part of the acidic components upstream of the membrane
module, to remove dust particles by filtration and to superheat
the feed gas upstream of the membrane module to prevent con-
densation.
3 Shut-down of the unit by purging with ambient air in order to
remove any remaining flue gas and prevent harmful condensa-
tion.
Adhering to this procedure, the good separation performance
of the pilot plant equipped with PolyActiveTM multilayer thin film
composite membrane was demonstrated over extended periods
of time. The decrease in separation performance for the second
experiment could clearly be attributed to an instrumentation fail-
ure resulting in a pilot plant shut-down without subsequent air
64 J. Pohlmann et al. / International Journal of Greenhouse Gas Control 53 (2016) 56–64
purging. Whilst such failures are tolerable in pilot plant experi-
ments, they are not for industrial scale operation. Additional control
and operating procedures would have to be implemented in order
to prevent this from happening. One such measure would be the
integration of the membrane unit control into the overall power
plant control. For pilot plant experiments this was not possible due
to operational security concerns.
The simulation model was generally found to be in good agree-
ment with the experimental data. However, deviations exist until
an equilibrium state is reached. This especially pronounced for
the recompressed permeate. One probable cause is the incorrect
simulation of the liquid ring pump as an isothermal compressor.
Future work on the simulation model will include optimization
of this part of the simulation model in order to properly describe
the non-equilibrium periods during pilot plant start-up, shut-down
and changes imposed during operation. It also is expected that the
modified model helps to more thoroughly understand the complex
interaction of variables in these dynamic operating periods.
Membrane processes using PolyActiveTM membranes seem to
be well suited for post combustion CO2 separation. E.g., a CO2 purity
68.2 mol-% in the permeate at a CO2 recovery of 42.7 % could be
realised for the standard conditions of the second experiment with
the employed one stage process. If care is taken with the neces-
sary flue gas pre-treatment, the membrane material is stable in the
intermittent operating scenarios typical for Germany’s coal fired
power plants. Process design considerations will include two stage
operation, i.e. recompressing the 1st stage permeate and supplying
it as feed to a second membrane module. The CO2 composition in
the permeate of such a second membrane module can be adjusted
to values in excess of 95 mol-% (Brinkmann et al., 2015a).
Acknowledgements
The authors would like to acknowledge the funding given by the
German Federal Ministry for Economic Affairs and Energy to finance
the research project METPORE II (funding identifier 03ET2016). In
addition, the authors would like to give thanks to EnBW and RWE
for their generous financial contribution to the project, for provid-
ing us with the opportunity to carry out the experiments in their
facilities as well as for the exceptional technical support given dur-
ing the operation of the experiments. The authors would also like to
thank the members of the project consortium (Mr. Christoph Bless-
ing of EnBW, Dr. Holger Dörr of KIT, Dr. Natividad Jordan Escalona
of RWE, Mrs. Marijke de Graaff of EnBW, Dr. Akos Tota of Linde AG
and Dr. Dr. Li Zhao of Forschungszentrum Jülich).
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