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Review article
a r t i c l e
i n f o
Article history:
Received 16 July 2008
Received in revised form
10 September 2008
Accepted 11 September 2008
Available online 19 September 2008
Keywords:
Immobilized liquid membrane
Supported liquid membrane
Gas separation
Vapor separation
Preparation
Performance
Materials
a b s t r a c t
A review on developments of liquid membranes (LMs) in the eld of gas and vapor separation of the
last 16 years is presented. Liquid membrane congurations employing supports, i.e. immobilized, supported and contained liquid membranes are focussed and detailed information on the respective materials,
i.e. supports (supplier, type, thickness, pore width, porosity, tortuosity), liquids and carriers, are presented together with their specic separation tasks. Performance of different LMs in terms of permeability
and selectivity as well as stability (duration of testing, applied differential pressures) are compared and
discussed. Finally, different preparation methods of LMs are illustrated.
2008 Elsevier B.V. All rights reserved.
Contents
1.
2.
3.
4.
5.
6.
7.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Liquid membrane congurations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mass transfer in liquid membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Materials for LM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.
Supports for LM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.
Liquids and carriers for LM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Performance of LM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Preparation of LM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary of liquid membrane review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Abbreviations: BEHA, bis(2-ethylhexyl)amine; CA, carbonic anhydrase; CAN, cellulose acetate-nitrate; CLM, contained liquid membrane; CUN, cuprophan; DAE,
diaminoethane; DBC, dibenzo-18-crown-6; DEA, diethanolamine; DETA, diethylenetriamine; DEYA, diethylamine; DGA, diglycolamine; DIPA, diisopropanolamine;
EDA, ethylenediamine; ELM, emulsion liquid membrane; FS, at sheet; HF, hollow
ber; IL, ionic liquid; ILM, immobilized liquid membrane; LiAlO2 , lithium aluminate;
LM, liquid membrane; MEA, monoethanolamine; MS, molten salt; NA, not available;
PAA, porous anodic alumina; PAMAM, polyamidoamine dendrimer; PAN, polyacrylonitrile; PEG, polyethyleneglycol; PES, polyethersulfone; PP, polypropylene;
PS, polysulfone; PTMSP, polytrimethylsilylpropyne; PVDF, polyvinylidinediuoride;
SLM, supported liquid membrane; TEG, triethyleneglycol.
Corresponding author. Tel.: +49 241 8 09 05 83; fax: +49 241 8 09 22 52.
E-mail addresses: orian.krull@avt.rwth-aachen.de (F.F. Krull),
clemens.fritzmann@avt.rwth-aachen.de (C. Fritzmann),
thomas.melin@avt.rwth-aachen.de (T. Melin).
0376-7388/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2008.09.018
509
510
510
511
511
513
515
517
518
518
518
1. Introduction
For more than 30 years now, liquid membranes have been in
focus of research. Since diffusivities in liquids in comparison to
solids are higher by several orders of magnitude, enhanced permeabilities of liquid in comparison to solid membranes can be
expected.
Investigated applications of liquid membranes comprise the
separation/concentration of ions [1,2], the separation of liquid feeds
[3] and the separation of gases or vapors which are subject of the
review at hand.
Several reviews have been written on liquid membrane-based
separations [49]. However, to our knowledge only one of these
510
511
A different approach to increase or obtain a sorption selectivity of the membrane liquid is given by the use of homogeneous
catalysts (Fig. 3).
In contrast to a carrier, the catalyst increases the solubility of a
gas inside the membrane liquid due to conversion of the gas to a
product, which diffuses towards the permeate phase. However, in
this case a back-diffusion of reaction products cannot be excluded
since the partial pressure for the product in the gas phases is very
low at both sides of the membrane.
The combination of the unit operations homogeneous catalysis
and gas separation into one clearly leads to process integration.
To present, homogeneous catalysis inside an ILM has only been
investigated by Carlin et al. [15,16].
4. Materials for LM
As in every membrane process, separation characteristics of the
process are determined by the properties of the membrane material. Hence, the materials of LM, i.e. liquids and carriers as well as
the supports are subject of the Sections 4.2 and 4.1, respectively.
4.1. Supports for LM
As shown in Section 3, the liquid and carriers are responsible
for LM properties in terms of permeability and selectivity, while
the choice of the support merely affects the permeability by its
porosity. However, the right choice of support ensures sufcient
stability of the LM conguration.
In Tables 1 and 2 the separation tasks, congurations and
employed supports reported in the literature of the last 16 years
are given chronologically, starting with the most recently reported
conguration.
As can be seen from Tables 1 and 2, the vast majority of supports are at sheet polymeric supports. Only some authors employ
polymeric hollow ber supports [22,24,33,35] and Huang et al. and
Baltus et al. employ a ceramic support [17,25].
For preparation of an ILM, the support must be wettable by the
membrane liquid whereas it should be non-wettable for preparation of an SLM. Further, the support should be chemically and
thermally inert to avoid a mechanical breakdown of the membrane
function. Wettability is ensured if hydrophobic supports are combined with organic liquids or hydrophilic liquids with hydrophilic
supports. The latter represents the majority in the reported congurations.
The support mainly inuences the mechanical and long-term
stability of a LM conguration. According to the so-called bubble
point equation, which is derived from a thermodynamical point
512
Fig. 3. ILM with simultaneous gas or vapor separation and catalytic reaction.
Table 1
Separation tasks, congurations and supports of liquid membranes.
Separation task
Conguration
Support
Ref.
ILM
ILM (SLM)
[17]
[18]
CO2 /He
SO2 /N2 , SO2 /CH4 , SO2 /CO2
H2 O vapor/air/VOC
CO2 /air
H2 , CO, O2 , N2
CO2 /air
CO2 , N2
CO2 /CH4
CO2 /N2 and CO2 /CH4
CO2 /CH4 /H2 , water vapor/air, benzene vapor/cyclohexane vapor
ILM
ILM
ILM (SLM)
CLM
ILM
CLM
ILM
ILM
ILM
ILM
C3 H6 /C3 H8
ILM
C4 H8 /C4 H10
CO2 /N2
H2 S/CO2 , H2 S/CH4
CO2 /N2
CO2 /CH4
ILM
ILM
ILM
ILM
ILM
PAA
PTFE support for ILM which is sandwiched between two
hydrophobic PTFE supports
PES, PS
Hydrophilic PES
Hydrophilic CA, hydrophobic PVDF
PP
NA
PP
PAA
Hydrophilic PVDF
PES
Hydrophilic PTFE (ILM) supported on hydrophobic PVDF
support
Hydrophilic PTFE (ILM) supported on hydrophobic PVDF
support
Hydrophilized PVDF
Hydrophilized PVDF, PP
PP
Hydrophilic Supports: PAN, CUN, hydrophilized PS bers
Hydrophilic PTFE support (ILM) supported on PVDF support
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
Table 2
Separation tasks, congurations and supports of liquid membranes continued.
Separation task
Conguration
Support
Ref.
ILM
[35]
Water vapor/air
ILM
SO2 /air
CO2 /N2
ILM
ILM
CO2 /air
CO2 /N2
SO2 /N2
CO2 /N2
CO2 /CH4
CO2 /CH4 /H2
CO2 /C2 H6
SO2 /N2
CO2 /CH4
O2 /N2 (air)
ILM
ILM
ILM
ILM
ILM
ILM/SLM
ILM
ILM
ILM
ILM
ILM
Hydrophilized PVDF,
hydrophilized PP, PAN
bers, hydrophilized PS
bers
Hydrophilic PTFE support
(ILM) supported on PVDF
support
Porous LiAlO2
Hydrophilic PVDF,
hydrophilized PP
Hydrophilic CAN
Hydrophilic PVDF
Hydrophilic PVDF
Hydrophilic CAN
Hydrophilic PVDF
PP (ILM)/PTMSP (SLM)
PP
NA
PP
Stainless steel woven wire
mesh
Stainless steel woven wire
mesh, woven zirconia cloth
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]
[49]
p =
4kp cos()
,
dp
(1)
a small contact angle between support and liquid (ILM conguration) and a small pore diameter dp of the support ensure higher
achievable differential pressures p across the membrane [50,51].
With increasing interfacial tension between liquid and gas phase
higher differential pressures are possible. The factor kp denotes
deviation of the experimental pressure from the theoretical bubble
point, i.e. 0 < kp 1.
In Tables 36 , details on the supports of the reported conguration in the literature are presented.
The thickness of the liquid membrane most often corresponds
to the thickness of the support and lies between 25 and 380 m.
Exceptions to this are given by the congurations of Gan et al. [23].
An additional layer of ionic liquid is placed on top of the fully wetted
support to avoid gas permeance through the solid polymeric support. This example shows that the gas permeability of the polymeric
support itself must be negligible if liquid membrane permeability
is to be determined and highly selective membrane congurations
are to be achieved.
Chen et al. investigated the effect of liquid membrane thickness
on permeability [38]. Details on this will be given in Section 6.
513
Table 3
Supports for liquid membranes.
Support material
Supplier/type
Shape
Thickness [m]
Ref.
PAA
PTFE support for ILM which is
sandwiched between two
hydrophobic PTFE supports
PS, PES
Hydrophilic PES
Hydrophilic CA, Hydrophobic PVDF
PP
Whatman
NA
FS
FS
60
35
[17]
[18]
FS
FS
FS
HF
[19]
[20]
[21]
[22]
FS
FS
167 + 118
250
[23]
[24]
FS
FS
FS
FS
60
100
152
3555
[25]
[26]
[27]
[28]
FS
4570
[29]
FS
FS
FS
100
PVDF: 100, PP: 25
25
[30]
[31]
[32]
NA
PP
PAA
Hydrophilic PVDF
PES
Hydrophilic PTFE (ILM) supported
on hydrophobic PVDF support
Hydrophilic PTFE (ILM) supported
on hydrophobic PVDF support
Hydrophilized PVDF
Hydrophilized PVDF, PP
PP
Yamanouchi et al. [28] and Duan et al. [29] report about different membrane congurations employing the same support for
different separation tasks. Hence a range of thicknesses is given in
Table 3.
The pore width of the supports lies between 0.005 and 13 m.
Porosity of the supports ranges from 0.4 and 0.83 while tortuosity
if determined ranges from 1.0 to 3.05.
4.2. Liquids and carriers for LM
Tables 7 and 8 show the different liquids and carriers employed
in the LM congurations of the last 16 years.
In gas separations, the long-term stability of a LM conguration is mainly dependent on the volatility of the membrane
liquid. Hence, low to non-volatile liquids such as glycerol or tri-
= eM/RTdp
(2)
the vapor pressure pv inside a porous support is lower in comparison to the normal vapor pressure p0v for a smaller pore diameter dp
of an employed support ([52], p. 58). The terms M and represent
Table 4
Supports for liquid membranes continued.
Support material
Supplier/type
Shape
Thickness [m]
Ref.
NA
HF
[33]
FS
Porous LiAlO2
Hydrophilic PVDF, hydrophilized PP
Hydrophilic CAN
Hydrophilic PVDF
Hydrophilic PVDF
Hydrophilic CAN
Hydrophilic PVDF
PP (ILM)/PTMSP (SLM)
PP
NA
PP
Stainless steel woven wire mesh
Stainless steel woven wire mesh
Woven zirconia cloth
[34]
FS, HF
[35]
FS
35
[36]
FS
FS
NA
PVDF: 100, PP: 25
[37]
[38]
FS
FS
FS
FS
FS
FS
FS
FS
FS
FS
FS
150
100
100
150
100
PP: 25, PTMSP: NA
25
NA
25
200
Wire mesh: 200,
Ceramic cloth: 380
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]
[49]
514
Table 5
Supports for liquid membranes continued.
Support material
Porosity
Tortuosity
Ref.
PAA
PTFE support for ILM which is sandwiched
between two hydrophobic PTFE supports
PES, PS
Hydrophilic PES
Hydrophilic CA, hydrophobic PVDF
PP
NA
PP
PAA
Hydrophilic PVDF
PES
Hydrophilic PTFE (ILM) supported PVDF
support on hydrophobic
Hydrophilic PTFE (ILM) supported on
hydrophobic PVDF support
Hydrophilized PVDF
Hydrophilized PVDF, PP
PP
Hydrophilic supports: PAN,
CUN, hydrophilized PS bers
0.1
0.1
NA
0.71
1
NA
[17]
[18]
0.2
0.22
0.22 (CA), 0.15 (PVDF)
0.04
NA
0.04
0.02
0.10
0.20
1.00
0.750.85
0.8
NA
0.4
NA
0.4
NA
NA
0.8
0.83
NA
NA
NA
NA
NA
NA
1.0
NA
NA
NA
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
1.00
0.83
NA
[29]
0.10
PVDF: 0.10
NA
PAN: NA,
CUN: 0.005,
PS: 0.10 and 0.20
0.7
PVDF: 0.7, PP: 0.45
0.5
PAN: NA,
CUN: 0.60.7,
PS: 0.30.4 and 0.70.8
2.58
PVDF: 2.58, PP: 2.54
1.25
NA
[30]
[31]
[32]
[33]
Table 6
Supports for liquid membranes continued.
Support material
Porosity
Tortuosity
Ref.
1.00
PVDF: 0.10,
Celgard: 0.08,
PAN: 70000 MWCO, PS: 0.70
1.00
NA
PVDF: 0.10,
PP: 0.04
0.80
0.10
NA
0.80
0.10
Celgard: 0.05 0.125, PTMSP: NA
0.075 0.25
NA
0.04
4.013.0
4.013.0
0.83
PVDF: 0.7, PP: 0.45,
PAN: NA, PS: 0.30.4
NA
PVDF: 2.58, PP: 2.54,
PAN: NA, PS: NA
[34]
[35]
0.83
NA
PVDF: 0.7,
PP: 0.45
0.82
0.7
0.63
NA
0.7
PP: 0.5, PTMSP: NA
0.45
NA
0.45
NA
NA
NA
NA
PVDF: 2.58,
PP: 2.62
3.05
2.58
2.61
3.05
3.233.35
PP: 1.25, PTMSP: NA
1.75
NA
2.1
NA
NA
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]
[49]
Table 7
Separation tasks, liquids and carriers of liquid membranes; brackets in carrier column indicate that authors report on experimental results obtained with pure liquids as well
as with liquidcarrier mixtures.
Separation task
Liquid
Carrier
Ref.
Functionalized liquid
[17]
[18]
CO2 /He
SO2 /N2 , SO2 /CH4 , SO2 /CO2
H2 O vapor/air/VOC
CO2 /air
H2 , CO, O2 , N2
CO2 /air
CO2 , N2
CO2 /CH4
CO2 /N2 and CO2 /CH4
CO2 /CH4 /H2 , water vapor/air, benzene
vapor/cyclohexane vapor
C3 H6 /C3 H8
C4 H8 /C4 H10
CO2 /N2
[hmim][Tf2N]
[emim][BF4 ], [bmim][BF4 ], [hmim][BF4 ], [bmim][PF6 ], [bmim][Tf2N]
LiCl H2 O
H2 O
ILs: [C4-mim][Tf2N], [C10-mim][Tf2N],[N881][Tf2N], [C8Py][Tf2N]
H2 O
ILs: [C4-mim][Tf2N], [C8F13-mim][Tf2N]
H2 O
ILs: [C2-mim][Tf2N], [C2-mim][CF3SO3],[C2-mim][dca], [thtdp][Cl]
IL [pmim][I]
Functionalized liquid,
except [C4mim][Tf2N]
- no carrier
None
None
None
CA, DEA, NaHCO3
None
DEA
None
DETA,DAE, DEYA, BEHA
None
(K2 CO3 )
H2 S/CO2 , H2 S/CH4
TEG
Glycerol
Glycerol carbonate
AgBF4 or AgNO3
AgNO3
PAMAM, sodium
glycinate
Functionalized liquid
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
515
Table 8
Separation tasks, liquids and carriers of liquid membranes continued; brackets in carrier column indicate that authors report on experimental results obtained with pure
liquids as well as with liquidcarrier mixtures.
Separation task
Liquid
Carrier
Ref.
CO2 /N2
CO2 /CH4
CO2 /N2 , CO2 /O2
Water vapor/air
SO2 /air
CO2 /N2
CO2 /air
CO2 /N2
SO2 /N2
CO2 /N2
CO2 /CH4
CO2 /CH4 /H2
Glycerol
TEG, DGA
PAMAM
TEG, PEG
MS: 0.78 Li2 SO4 , 0.135 K2 SO4 and 0.085 Na2 SO4
Glycerol
H2 O
Glycerol
H2 O
H2 O
H2 O
MS hydrates: tetramethylammmonium
uoride tetrahydride, tetraethylammonium
acetate tetrahydrate
PEG
PEG
PEG-400
MS: anhydrous LiNO3 , dry NaNO3
MS: LiNO3 and ZnCl2
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
DEA
DEA
DEA, DIPA
Functionalized liquid
Functionalized liquid
[45]
[46]
[47]
[48]
[49]
CO2 /C2 H6
SO2 /N2
CO2 /CH4
O2 /N2 (air)
NH3 /N2 , NH3 /H2
the molar mass and the density of the liquid, while the terms R and
T denote the universal gas constant and the absolute temperature
in Kelvin, respectively.
In combination with glycerol, feed gas humidication also
decreases the viscosity of the membrane phase since the viscosity of glycerol is highly dependent on the water content of a
glycerolwater mixture [53,54]. Thus, the diffusivity of dissolved
species in glycerol is enhanced resulting in higher permeabilities.
Due to the difculty in nding liquids displaying a sorptionselectivity for different gases, carrier species are often employed,
which should be dissolvable in the liquid to a high extent (cf. e.g.
[24,29]). The higher the solubility of a carrier species, the higher the
allowable feed partial pressure of a desired permeant before saturation in carrier species takes place. In the past 30 years, several
review articles on facilitated transport concepts in liquid membranes by the use of carriers have been written, e.g. [7,9].
In comparison to conventional liquids (organic or aqueous mixtures) liquid molten salts offer the possibility of an intrinsic carrier
function, i.e. one of the salt ions acts like a carrier [32,44,49]. In the
following, these liquids are referred to as functionalized liquids.
5. Performance of LM
In Tables 912 the different reported gas and vapor separation
tasks and the performance of the employed liquid membrane congurations in terms of permeability, selectivity, pressure stability
and long-term stability are given.
The most encountered separation task is the removal of CO2
from gas streams containing CH4 or air. About 2/3 of the reviewed
Table 9
Performance of liquid membranes.
Separation task
Selectivity
Flux/permeability
Flux/permeability unit
Ref.
GPU
(1E6 cm3 (STP)cm/cm2 s cm
HG)
Barrer
Barrer
Barrer
[17]
H2 O vapor/air/VOC
CO2 /air
H2 , CO, O2 , N2
CO2 /air
CO2 , N2
kg/m2 s
mol/(m2 s Pa)
Barrer
mol/(m2 s Pa)
mol/(bar cm2 s)
[21]
[22]
[23]
[24]
[25]
CO2 /CH4
mol/(m2 ) s kPa)
[26]
Barrer
[27]
H2 O vapor: 1.14E4
CO2 : 1 108 to5 108
H2 : 151250, CO: 01450
CO2 : 1.25 108 to5.01 108
N2 : 2.1 1011 to3.2 1011 , CO2 :
1.5 109 to4.0 109
CO2 : 2 107 to1.7 106 , CH4 :
2 109 to9 109
N2 : 1048, CO2 : 3501000, CH4 :
3194
CO2 : 3 108
[28]
[29]
[30]
[31]
Barrer
[32]
[33]
[34]
CO2 /CH4
CO2 /He
SO2 /N2 , SO2 /CH4 , SO2 /CO2
H2 S/CO2 , H2 S/CH4
CO2 /N2
CO2 /CH4
CO2 : 5002500
CO2 : 7441200
SO2 : 72809350
[18]
[19]
[20]
516
Table 10
Performance of liquid membranes continued.
Separation task
Selectivity
Flux/permeability
Flux/permeability unit
Ref.
Barrer
[35]
Water vapor/air
SO2 /air
CO2 /N2
CO2 /air
CO2 /N2
SO2 /N2
CO2 /N2
CO2 /CH4
CO2 /CH4 /
H2
CO2 /C2 H6
SO2 /N2
CO2 /CH4
O2 /
N2 (air)
NH3 /N2
NH3 /H2
cm (STP)cm/(cm s cmHg)
kmol/m2 s
scm3 /(cm2 s cmHg)
cm3 /(cm2 s cmHg)
cm3 /(cm2 s cmHg)
mol/(m2 s kPa)
mol/(cm2 s)
cm3 /(cm2 s cmHg)
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
ILM: barrer
[44]
m3 m/(m2 s kPa)
m3 m/(m2 s kPa)
[45]
[46]
Barrer
[47]
Barrer
[48]
Barrer
[49]
articles report on CO2 separations, stressing the industrial relevance of this separation task. Other separation tasks are given by the
removal of SO2 , H2 S and NH3 . Water vapor transport is investigated
by Ito [36] and Yamanouchi et al. [28] who also report on separation
of benzene vapor from cyclohexane vapor. Finally, alkene/alkane
separations are examined by different authors [29,30]. This separation task as well as SO2 removal are of major industrial relevance.
Since generally only very few reports and no review article on
membrane-based SO2 removal are available, the number of ve
reports cited in the review at hand stands out.
Table 11
Performance of liquid membranes continued.
Separation task
Differential pressure
Long-term stability
Ref.
112 kPa
0
15.7 psi
Atmospheric
NA
More than 260 days
Up to 125 C
NA
[17]
[18]
[19]
[20]
Atmospheric
Atmospheric
7 bar
Atmospheric
17 psia upstream, 12 psia
downstream
160 kPa feed, 135 kPa Sweep 0,25 bar ptrans
020 kPa
Atmospheric feed, 0.11.3 kPa
vacuum permeate
Atmospheric feed, 1.3 kPa vacuum
permeate
2 atm
6 psi
None
35.852.4 kPa
NA
50 days
Stable up to 10 bar during experiments
5 days
NA
[21]
[22]
[23]
[24]
[25]
NA
[26]
NA
NA
[27]
[28]
23 weeks
[29]
3 weeks
More than a week
NA
Up to 300 h at 1.27 atm 40 m
glycine-Na-glycerol ILM
[30]
[31]
[32]
[33]
CO2 /CH4
CO2 /N2 and CO2 /CH4
CO2 /CH4 /H2 , water vapor/air, benzene vapor/cyclohexane vapor
C3 H6 /C3 H8
C4 H8 /C4 H10
CO2 /N2
H2 S/CO2 , H2 S/CH4
CO2 /N2
517
Table 12
Performance of liquid membranes continued.
Separation task
Differential pressure
Long-term stability
Ref.
CO2 /CH4
CO2 /N2 , CO2 /O2
Water vapor/air
SO2 /air
CO2 /N2
CO2 /air
CO2 /N2
[34]
[35]
[36]
[37]
[38]
[39]
[40]
SO2 /N2
CO2 /N2
CO2 /CH4
CO2 /CH4 /H2
CO2 /C2 H6
SO2 /N2
CO2 /CH4
O2 /N2 (air)
Atmospheric
Atmospheric feed /560 mmHg sweep
Atmospheric
400 cmHg ILM, 545 cmHg SLM
Atmospheric
Atmospheric
1 atm
76 cmHg
80 cmHg
the fact that state of the art polymeric membrane selectivity for
CO2 ranges between 5 and 45 with a permeability of up to 600
barrer [55], various of the reported LM congurations prove to be
comparable. For example Hanioka et al. report permeabilities of
5002500 barrer with selectivities of 10120 for the separation of
CO2 and CH4 even exceeding the standards of polymeric membranes
[18].
For separation of propylene/propane mixtures a similar result
is achieved comparing LM congurations to data given in a review
article by Burns and Koros [56]. Selectivity of polymer membranes
for this task ranges from 1.4 to 27 with permeabilities of up to
6600 barrer. Duan et al. report on permeabilities of 801000 barrer
with selectivities of 2570 for this separation task [29].
However, two aspects need to be considered when comparing
the congurations cited beforehand. On the one hand, in most cases
high selectivity values of a membrane most often go along with low
permeability values. Thus, both values have to be taken into account
when comparing two specic membrane congurations. On the
other hand, the unit Barrer represents permeability of a membrane
with respect to its thickness. While for a thick membrane its permeability given in Barrer might be high, its absolute ux might be low.
Thus, a comparison of absolute ux values across two membranes
should be the comparison of choice. A detailed comparison of ux
values of different liquid as well as solid membrane congurations
lies beyond the scope of the work at hand. A comparison of absolute uxes between polymeric and liquid membranes even proves
to be impossible since also for polymeric membranes information
on membrane thicknesses is lacking in the review article of Burns
et al. and Powell et al. However, since in most congurations, LM
thickness still is limited to the thickness of the employed supports,
a minimization of LM thickness going along with a maximization
of ux remains a desirable aim.
Most of the reported liquid membrane congurations work at
atmospheric conditions or slightly elevated pressures. The highest
reported differential pressure is 7 bar [23].
Data concerning the long-term stability of the membrane congurations are only given by some authors. Here the most stable
conguration shows long-term performance for about 260 days
[18].
Although, regarding permeability and selectivity, LM performance seems to have improved very much in the last 16 years,
their long-term stability still constitutes the major challenge when
aiming at industrial application.
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]
[49]
6. Preparation of LM
After the materials for preparation of a liquid membrane conguration have been chosen, the preparation itself is carried out. In
general, an ex situ and in situ preparation of LM can be differentiated.
In the ex situ preparation, a support is wetted with the membrane liquid by soaking or impregnation. Depending on the pore
size and the wettability of the support, the time for preparation differs between hours or even days. After successful wetting
of the support, excess liquid is normally wiped off to obtain a
thin membrane. Generally the membrane thickness corresponds
to the support thickness, since the support is totally wetted. This
method represents by far the most applied preparation method
for LM.
Chen et al. also apply the ex situ preparation method, but report
on a wicking method to partially wet a at support with a membrane liquid and thus adjust the liquid layer thickness [38]. A at
support is put into contact with glycerol as a membrane liquid,
which is intruding into the pores of the support due to capillary
forces. Depending on the wetting time, a different liquid layer thickness is achieved.
In general, the use of feed gas humidication somehow impairs
the effect of a lower membrane thickness, since water vapor
might condense inside open pore spaces of the partially wetted
support representing a diffusion resistance for permeating gas
species.
In the in situ membrane preparation, the porous support is
mounted to a membrane module and contacted with membrane
liquid inside the module. Again, the liquid wets the support due
to capillary forces. After some time of impregnation, the liquid
is expelled out of the lumen of the membrane module via a gas
stream. Such membrane preparation is reported by Chen et al. [33]
for preparation of hollow ber liquid membrane congurations. Pez
et al. also report about an in situ preparation of LM [48] employing
liquid molten salts as membrane phase, which are liquid at temperatures well above room temperature. To prepare these membranes,
salt granules are placed on top of a wire mesh or a zirconia cloth
inside a membrane module. The closed module is then heated up
above the melting temperature of the salt granules, which become
liquid and wet the pores of the support forming a liquid membrane.
Since some of the employed salts are oxygen and water sensitive,
the whole equipment is inertised with argon gas.
518
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