CO2 From Flue Gas

Journal of Membrane Science 279 (2006) 149
Review
Polymeric CO2/N2 gas separation membranes for the capture of carbon dioxide from power plant ue gases
Clem E. Powell, Greg G. Qiao
Cooperative Research Centre for Greenhouse Gas Technologies, Department of Chemical and Biomolecular Engineering, University of Melbourne, Australia Received 15 July 2005; received in revised form 23 November 2005; accepted 23 December 2005 Available online 17 February 2006
Abstract Global warming has been identied as one of the worlds major environmental issues. While it is impossible to completely stop the effects of anthropological global warming, it is possible to mitigate these effects via a variety of options. One such option is the reduction of greenhouse gas emissions by the capture of carbon dioxide from ue gases followed by underground sequestration. For this technology to become widespread, new methods of capturing carbon dioxide must be devised. While capture of carbon dioxide with amine solvents is the most mature technology, another possible contender is gas separation membranes. This review will focus on novel materials for gas separation. In particular, polymeric gas separation membranes are examined. Possible design strategies, synthesis, fabrication and role of novel materials are discussed. 2006 Elsevier B.V. All rights reserved.
Keywords: Geosequestration; Gas separation; Membranes; Polymeric; Carbon dioxide; Nitrogen; Polysulfones; Polyimides; Polycarbonates; Polyarylates; Polypyrrolones
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1. Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2. Carbon capture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Gas separation membranes for CO2 /N2 separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1. Synthetic strategies for polymeric gas separation membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2. Polymer structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.1. Polyarylates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.2. Polycarbonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.3. Polyimides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.4. Polypyrrolones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.5. Polysulfones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.6. Copolymers and polymer blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3. Pressure/temperature effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4. Cross-linking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5. Mixed-matrix membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6. Asymmetric membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Appendix A . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.1. Polyacetylenes (Figs. A1A3) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.2. Poly(arylene ether) (Fig. A4) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.3. Polyarylates (Figs. A5A7) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 2 4 5 5 6 9 9 10 11 13 14 17 19 20 22 23 24 24 25 26
2.
3.
Corresponding author. Tel.: +61 3 8344 8665; fax: +61 3 8344 4153. E-mail address: gregghq@unimelb.edu.au (G.G. Qiao).
0376-7388/$ see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.memsci.2005.12.062
C.E. Powell, G.G. Qiao / Journal of Membrane Science 279 (2006) 149
A.4. Polycarbonates (Figs. A8A10) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.5. Poly(ethylene oxide) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.6. Polyimides (Figs. A11A15) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.7. 6FDA-based polyimides (Fig. A16). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.8. Poly(phenylene oxide)s (Fig. A17) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.9. Poly(pyrrolone) (Fig. A18) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.10. Polysulfones (Figs. A19A22) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.11. Others (Figs. A23A27) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.12. Copolymers and polymer blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.13. Cross-linking polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
28 29 30 34 36 36 37 40 42 44 45
1. Introduction Anthropogenic climate change is rapidly becoming one of the major issues in environmental science. Global temperatures are projected to rise between 1.4 and 5.8 C by 2100 in the absence of climate change policies [1]. This increase in global temperatures is likely to cause a number of negative effects; including rising sea levels, changes in ecosystems, loss of biodiversity and reduction in crop yields [2]. These effects can be partially alleviated by reductions in emissions of greenhouse gases. Reduction of greenhouse gas emissions can occur in a number of ways; such as improvements in energy efciency, increased use of non-fossil fuel power sources, improved soil management and the geological sequestration of carbon dioxide from signicant greenhouse gas producing point sources [3]. Membranes have been investigated for over 150 years [4,5], and since 1980 gas separation membranes have been used commercially [6]. Gas separation membranes are used in a number of industrial processes; such as the production of oxygen enriched air, separation of CO2 and H2 O from natural gas, purication of H2 , and recovery of vapours from vent gases. A number of reviews examining gas separation membranes have been published [613]. Different strategies towards the construction of more efcient membranes have suggested by Koros and Mahajan [14]. Recent work has investigated the practicality of using gas separation membranes for the capture of carbon dioxide from power station ue gases. While cost effective carbon sequestration is a complex multi-faceted operation with many signicant hurdles to overcome (such as the cooling and compression of the ue gases prior to separation), there is a need to summarise the capabilities of membranes for carbon capture. There are a number of roles where gas separation membranes can be used to reduce emissions of greenhouse gases; however, this review will concentrate on the capture of carbon dioxide from ue gases and therefore focus on the use of membranes for the separation of carbon dioxide/nitrogen mixtures. A recent paper by Carapellucci and Milazzo looks at the possible use of membranes for carbon dioxide separation from ue gases from an engineers perspective [15]. This review will adopt a chemists view, examining the gas permeation properties of membranes in the light of their chemical structure. For this reason, attention will focus on dense lm membranes. Other membrane structures, such as hollow bre
and at asymmetric membranes will be discussed, but in less detail. A variant on polymeric membranes is a carbon membrane. These membranes are constructed by heating a polymeric membrane above its decomposition temperature. These membranes can give excellent performance, but tend to have signicant problems such as brittleness and cost. Because the mechanism of gas transport is very different in carbon membranes compared with polymeric membranes, carbon membranes will not be considered in this review. A number of useful references on carbon membranes have been published [1621]. 1.1. Theory What follows is a brief introduction to some terms required in the experimental characterization of gas transport properties of membranes; a more complete discussion can be found elsewhere [8,10]. Generally, gas molecules are transported through a polymeric membrane by a solutiondiffusion mechanism (other mechanisms included a molecular sieve effect and Knudsen diffusion). The relationship between permeability, diffusivity and solubility can be described by the following equation: P = DS where P is the permeability coefcient (cm3 (STP) cm2 s1 cmHg1 ; a measure of the ux of the membrane), D the diffusivity coefcient (cm2 s1 ; a measure of the mobility of the molecules within the membrane) and S is the solubility coefcient (cm3 (STP) cmHg1 ; a measure of the solubility of gas molecules within the membrane). The common measurement of P is the barrer (1010 cm3 (STP) cm2 s1 cmHg1 ). While P is a measure of a polymers permeability, a membranes permeance must also be measured. This is quantied using a term known as a gas permeation unit (GPU), commonly used to describe the gas transport of a membrane, as opposed to a membrane material. The GPU has a unit of 106 cm3 (STP) cm2 s1 cmHg1 . Experimentally, P is determined via the following relationship: Q P = l A p where l is the effective thickness of the membrane, Q the measure of the gas permeation rate through the membrane, A the surface
area of the membrane and p is the pressure difference across the membrane. The ideal selectivity of one gas A over another gas B, , is dened as PA = PB The dual mode sorption model provides another means of describing the sorption of gas molecules into a glassy membrane. The gas molecules are assumed to t into two categories; molecules absorbed directly into the polymer matrix and molecules absorbed into micro-cavities within the polymer matrix. The concentration of molecules absorbed in the polymer matrix, CD , and the concentration of molecules absorbed into micro-cavities, CH , can be described by the following equations: CD = kD p, C bp CH = H 1 + bp
the molecular sieves. Mixed-matrix membranes are discussed further in Section 2.5. The upper bound can be described by the following equation: A/B = A/B A/B PA
where A/B and A/B are constants for each gas pair. Freeman has suggested a theoretical model for this relationship [24]. From this model, A/B and A/B can be calculated from the following equations: A/B = and A/B = SA A/B S exp A/B b f SB A 1a RT dB dA
2
where kD is the Henrys Law coefcient, CH the hole saturation constant, p the pressure and b is the hole afnity constant. Hence, the total concentration of absorbed molecules can be described as C = kD p + CH bp 1 + bp
An experimental investigation of the dual-sorption model has been recently published by Chung and co-workers [22]. There appears to be a trade-off between selectivity and permeability, for example a highly selective membrane tends to have a low permeability. Robeson has suggested that the permeabilityselectivity trade-off possesses an upper bound [23]. Fig. 1 provides an example of this upper bound. Subsequent to the publication of Robesons paper, only a few examples of polymeric membranes have been published which exceed the upper bound. Koros and Mahajan have suggested that it may be possible to exceed the upper bound signicantly by the use of mixed-matrix membranes [14]. These membranes consist of a polymeric membrane with a large volume of sub-micromolecular sieves. This approach could combine the processability of membranes with the high performance characteristics of
where d is the kinetic diameters of gases A and B, S the solubility coefcient of gases A and B, a the constant equal to 0.64, and b and f are the constants depending on the polymer. The constant b = 9.2 and 11.5 cm2 s1 for rubbery and glassy polymers respectively. The value of f can vary by a very large degree, from 0 to 14,000 cal mol1 . The fractional free volume (FFV) is a measure of the theoretical volume of the polymer divided by the actual volume of the polymer. The fractional free volume is usually dened as V V0 V where V is the volume of the polymer per unit mass and V0 the volume per unit mass occupied by the polymer chains. Park and Paul have suggested a denition of FFV, one which assumes that the FFV is not constant for all gas types [25]: FFV = V (V0 )n (FFV)n = , V
K
(V ) =
k=1
nk (VW )k
where nk is a set of empirical factors which depend on gas n and substituent k. (VW )k is the van der Waals volume for substituent k. Using this revised FFV, the authors can get a good correlation between experimental permeabilities and permeabilities calculated with the following relationship: P = A exp B FFV
Fig. 1. Oxygennitrogen selectivity vs. oxygen permeability (from Ref. [23]).
where A and B are the constants for the gas. For carbon dioxide at 35 C and 10 atm pressure, A = 1750 and B = 0.860. For nitrogen at 35 C and 2 atm pressure, A = 112 and B = 0.967 [25]. Some attempts have been made to model the passage of carbon dioxide through a polymeric membrane via a solutiondiffusion mechanism [2630]. Gases, in these models, tend to move through gaps in the polymeric structurecalled the free volume. Because of movement of the polymer chains, a channel between gaps can be formed allowing gas molecules to jump from one gap to another. Through this jumping motion, gas molecules can effectively diffuse through the membrane structure. Selective transport of gases can be achieved by use of a
C.E. Powell, G.G. Qiao / Journal of Membrane Science 279 (2006) 149 Table 1 Examples of group contributions to permeabilities Group Volume 3) (A CO2 permeability (barrer) N2 permeability (barrer)
39.0
3.34
0.327
40.75 Fig. 2. Movement of CO2 through a 6FDAPDA membrane (from Ref. [27]).
0.021
0.00139
polymer which forms channels of a certain size. Large channels will allow faster diffusion of gases through a membrane at the cost of less selectivity between different gases; smaller channels will allow a much greater selectivity at the cost of lower permeation rates. A more complete discussion of gas transport through polymeric membranes has been published by Maier [8] (Figs. 2 and 3). Pavel and Shanks have performed a molecular dynamics study of the diffusion of carbon dioxide and oxygen through a variety of polyesters [31]. A relationship between calculated density and calculated diffusion was not observed. There was a relationship between the calculated diffusion coefcient and the calculated Voronoi free volume. The gas molecules were observed to travel through transient cavities through the polymer structure. The distribution of these holes had a signicant dependence on the conformation of the phenyl rings. The calculated diffusion coefcients followed a para > ortho > meta series. Another method to determine permeabilities theoretically is a group contribution approach [32,33]. The authors have used a number of literature polymers to calculate volume and permeability contributions for a large number of structural moieties commonly present in polymers used in the construction of gas separation membranes. The permeabilities can then be calculated using the following expression:
n
65.56
309.0
15.5
74.5
10.66
0.508
68.0
34.18
0.877
54.94
16.0
0.678
773.19 Data from Refs. [32,33].
278.7
27.5
ln P =
i=1
i ln Pi
where i is the volume fraction of group i, and Pi is the permeability contribution of group i.
One advantage of a group contribution approach is the ability to quickly examine the effects of structural alterations on permeabilities. Some examples of the volume and permeabilities of various groups are tabulated in Table 1. 1.2. Carbon capture Geological sequestration of carbon dioxide requires two separate steps: the rst is the capture of carbon dioxide, and the second is the transport and sequestration of the captured carbon dioxide. This review will only concentrate on the rst process; however, for an example of the sequestration aspect, a review of the Weyburn pilot project, located in Saskatchewan Canada, is informative [34]. A number of different techniques have been proposed for the capture of carbon dioxide. These include chemical absorption, physical absorption, pressure swing absorption,
Fig. 3. Movement of CO2 through the cavities of a 6FDAODA membrane (from Ref. [27]).
temperature swing absorption, cryogenic distillation and separation via membranes. Membranes are a low cost means of separating gases, when high purity gas streams are not vital. There are a number of issues associated with the capture of carbon dioxide from ue gases which limit the use of membranes. The concentration of carbon dioxide in ue gases is low, which means that large quantities of gases will need to be processed. The high temperatures of ue gases will rapidly destroy a membrane, so the gases need to be cooled to below 100 C, prior to membrane separation. Likewise, the membranes will need to be chemically resistant to the harsh chemicals contained within ue gases, or these chemicals will need to be removed prior to the membrane separation step. Additionally, creating a pressure difference across the membrane will require signicant amounts of power, which will in turn lower the thermal efciency of the power plant. White et al. have recently published a review on the geological sequestration of carbon dioxide, comprehensively covering both the capture and storage of carbon dioxide [35]. This review includes a brief discussion on the possibility of membrane separation of carbon dioxide. Also recently published is a US Department of Energy report examining membrane separation of carbon dioxide for the purposes of geological sequestration [18]. In addition to polymeric membranes, the report examines inorganic membranes in detail. The authors are unconvinced about the usefulness of polymeric membranes for the capture of carbon dioxide, citing their low productivities. Similar concerns are expressed by White et al. [35]. Baker has pointed out that the compression and cooling of ue gases prior to a membrane separation require significant amounts of energy, which in turn lowers the efciency of the power plant [6]. Conversely, a modelling study of polymeric membranes in gas turbine power plants by Carapellucci and Milazzo is more encouraging [15]. The authors nd that a multi-step polymeric membrane system can effectively separate out carbon dioxide from gas ues. A potential problem is identied; oxygen in waste gases can signicantly reduce the purity of the carbon dioxide gas stream because of the relatively high permeability of oxygen through membranes. This can be avoided in external combustion plants, where the excess oxygen is kept to a minimum. Kazama et al. have recently investigated the possible role of cardo polyimide membranes for the capture of carbon dioxide from ue gases [36]. It was found that polymeric gas separation membranes were less cost effective at capturing carbon dioxide than amine solvents from power plants; however this was reversed when steel works were examined. The signicant difference between the power plants and steel works was the concentration of carbon dioxide in the waste gas stream. While the composition of ue gases varies greatly depending on the fuel source, power plant and prior treatment, some general statements can be made. Flue gases tend to be oxidising and generally consist of N2 , O2 , H2 O, CO2 , SO2 , NOx and HCl. Table 2 lists typical components of untreated ue gases from eastern low-sulfur bituminous coal [37]. Conversely, CO2 can be separated from fuel gases prior to combustion. Fuel gases are generally reducing with CO, H2 , H2 O, CO2 and H2 S [35]. Addi-
Table 2 Typical non-nitrogen components of untreated ue gases from Eastern Low Sulfur Coal Species H2 O O2 CO2 Hg complexes CO Various hydrocarbons HCl SO2 SO3 NOx Data from Ref. [37]. Concentration 57% 34% 1516% 1 ppb 20 ppm 10 ppm 100 ppm 800 ppm 10 ppm 500 ppm
tionally, untreated ue gas streams also contain considerable particulate matter. Some industrial processes, such as the production of steel, produce ue gases with a considerably higher CO2 concentration. For a membrane to be useful for the capture of carbon dioxide, it should posses a number of properties, namely: high carbon dioxide permeability. high carbon dioxide/nitrogen selectivity, thermally and chemically robust, resistant to plasticisation, resistant to aging, cost effective, and able to be cheaply manufactured into different membrane modules.
Sakellaropoulos and co-workers have investigated the use of polysulfone and polyimide membranes for separation of CO2 /N2 from ue gases [38]. They conditioned the polymers with exposure to high pressure CO2 , which caused a signicant increase in the performance of the polyimide membrane; however, this effect tended to decay with time. Other potential uses for membranes in the sequestration of carbon dioxide, is the incorporation of membranes into a precombustion separation step. This technique works by reaction of hot steam and methane to form a carbon dioxide and hydrogen gas mixture. At this stage, the carbon dioxide can be separated from the hydrogen gas which is then used to produce energy. Baker has suggested using N2 /O2 separation membranes to produce oxygen enriched air which can then be used for combustion of fossil fuels [6]. Both of these techniques are attempts to increase the concentration of CO2 and overcome one of the factors which disadvantage gas separation membranes. 2. Gas separation membranes for CO2 /N2 separation 2.1. Synthetic strategies for polymeric gas separation membranes Polymers used for CO2 /N2 separation membranes have to meet certain criteria. One is their ability to permeate the gas
Fig. 4. Synthetic strategy for polymer structure used as CO2 separation membranes.
through the membrane; so a reasonable gas ux is achieved during separation. The second criterion is the separation of carbon dioxide from other gases. The third one is that the polymeric membrane needs to provide good thermal and mechanical properties; hence the separation can be conducted effectively and sometimes at elevated temperatures. The above criteria are commonly met by synthesis of a block polymer system as shown in Fig. 4. The copolymer usually processes a hard block and a soft block. The hard block can be synthesised by polymer with well-packed and more rigid structures; therefore it forms a glassy segment of the polymer chain. On the other hand, the soft block can be synthesised from a polymer with more exible chains and that can form rubbery segments on the polymer chain. When a polymeric membrane formed by use of these copolymers, glassy polymer segments will form a structural frame and provide mechanical support. If the hard block is formed by high temperature polymers such as polyimides, it can also provide better thermal resistance. On the other hand, the rubbery segments usually form continuous microdomains and the nature of the exible chain structure allows the transportation of gas; hence provide a good permeability. Usually the balance of the hard and soft block ratio provide the good separation without loss of permeability. The glass segments usually gave lower free volume while the rubbery segments provide higher free volumes. The high free volume means the better gas permeation. The high free volume can also by achieved by intruding bulky structures into the soft blocks. 2.2. Polymer structure This section aims to detail different polymers and their CO2 and N2 gas transport properties. Attention has been focused primarily on glassy section or block of the polymers in the scientic literature recently. Examples of polymers used in the construction of gas separation membranes include polyacetylenes [9], polyaniline [3942], poly(arylene ether)s [43], polyarylates [4447], polycarbonates [4852], polyetherimides [53,54], poly(ethylene oxide) [55,56], polyimides [5774], poly(phenylene oxide)s [7577], poly(pyrrolone)s [7882] and polysulfones [48,50,8394]. Examples of these polymers are displayed in Fig. 5. There is an extensive body of literature on
gas separation membranes, for this reason, some polymers are covered in more detail at the expense of others. Fig. 6 displays the literature values carbon dioxide permeability versus carbon dioxide/nitrogen selectivity of a large number of polymers. The displayed polymers have been selected from Appendix A and all have been measured at 35 C and the carbon dioxide permeability at 10 atm. A clear upper bound is observed. While the poly(imide ethylene oxide) and cross-linked poly(ethylene oxide)s can appear to give both very high permeabilities and selectivities, this may be due to the lower pressure at which they were measured, relative to many other polymers. For this reason, these polymers are not displayed in Fig. 6. Also missing are some of the extremely highly fractional free volume polymers. These have been neglected in the interests of clarity. Both the classes of polymers are discussed later in the text. Additionally, the results presented here are from pure gas measurements. Mixed gas tests would result in different values. While mixed gas data would give results more applicable to industrial applications, there is considerably more data on pure gas measurements. The permeability of carbon dioxide frequently shows a strong dependence on the carbon dioxide partial pressure, whereas the nitrogen permeability dependence is considerably less. The permeability tends to drop with increasing pressure. If the membrane is vulnerable to plasticisation, the permeability will reach a minimum, and then rise steeply with increased pressure. It should be noted that permeabilities can be altered considerably by conditioning, such as thermal annealing of the membrane; this is particularly pronounced in glassy polymers. This introduces difculties in comparing results which in turn reduces the utility of gas permeation tests as a tool for determining structure/activity relationships. For example, the carbon dioxide permeability of the polyimide 6FDAdurene has been determined by three different laboratories, with values ranging from 400 to 456 barrer [65,71,95]. Upon thermally annealing a 6FDAdurene membrane at 100 C for 7 h then 180 C for another 7 h, it led to a drop in permeability from 400 to 230 barrer [95]. Another important variable is the casting solvent used to form the membrane. Mohr and Paul, for example, have investigated the effect of varying the casting solvent on the permeability of poly(4-methyl-1-pentene) [96]. The carbon dioxide permeability was found to vary from 15.0 to 93.8 barrer depending on the casting solvent (see Table 3 for more details). Chung and co-workers have performed a study on the effect of cast-
Fig. 5. Example of polymeric structures.
ing solvents on the permeabilities of a copolyimide membrane [97]. Another important issue concerning gas separation membranes is the effect of impurities on the membranes. Pereira and Admassu have investigated the effect of impurities such as pump compressor oils on the performance of a number of gas separation membranes [98,99]. Glassy polymers are vulnerable to aging effects. This is particularly pronounced in thin lms. Huang and Paul have published a method of monitoring the aging effects on gas transport properties of glassy polymers [100].
Fig. 6. Selectivity vs. permeability of polymeric membranes.
Table 3 Effect of casting solvent on the gas transport properties of poly(4-methyl-1pentene) Casting solvent Chloroform p-Xylene cis-Decalin Cyclopentane Cyclohexane Carbon tetrachloride Crystallinity 57 62 65 41 51 56 P(CO2 ) 15.0 42.6 27.8 93.8 83.0 77.7 P(N2 ) 1.1 2.7 1.6 7.4 6.5 6.0 (CO2 /N2 ) 13.6 15.8 17.4 12.7 12.8 13.0
Permeabilities in barrer, pressure = 2 atm, temperature = 35 C. Data from Ref. [96].
Para substituted phenyl rings tend to give, relative to meta, signicantly higher permeabilities, usually at the cost of selectivity. Closely packed polymer chains tend to give better selectivity, at the cost of permeability. Modication of the regions of the polymer which form a gap between cavities, can in principle, be used to alter selectivity for different gas pairs. This may be achieved by the synthesis of polymers which consist of alternating bulky and at groups. A more complete discussion of this can be found elsewhere [8]. Improving the solubility ratio of a membrane is, conceptually, much simpler than improving the diffusion selectivity. Carbon dioxide is considerably more polarisable than nitrogen, allowing the addition of functional groups to interact with them and thus increase the solubility of carbon dioxide within the membrane. Increasing the solubility ratio of a polymer for carbon dioxide over nitrogen may allow the upper bound to be exceeded. Poly(ethylene oxide) is an example of a polymer with high carbon dioxide solubility. One disadvantage of a high solubility is that this tends to lead to increased rates of plasticisation. An investigation into the permeabilities and solubilities of carbon dioxide, nitrogen and various hydrocarbons in a variety of commercial rubbery polymer membranes has been conducted by Freeman and co-workers [104]. The insertion of bulky substituents into the peripheral polymer backbones should disrupt efcient packing of the polymeric chains, leading to an increase in the permeabilities and a loss of selectivities. A number of different polymers have been investigated for this effect. The effect of incorporating bulky substituents into bisphenol A polycarbonate has been investigated by Muruganandam and Paul [52]. Relative to bisphenol A polycarbonate, tetramethyl- and tetrachloro-bisphenol A polycarbonate show greater permeabilities, with reduced selectivities. Tetrabromobisphenol A polycarbonate exhibits better selectivities, at the cost of a slightly reduced permeability. Tanaka et al. have investigated the effect of methyl substituents on the gas permeability and solubility coefcients of 6FDA-based polyimides [71]. A series of methyl-containing para- and meta-phenyl diamines have been reacted with 4,4 (hexauroisopropylidene)diphthalic anhydride to give a range of polyimides. As the number of methyl groups increases (from zero to four) a signicant increase in the carbon dioxide permeability is observed (from 9.20 to 440 barrer). As expected, a decrease in the carbon dioxide/nitrogen selectivity is also observed upon the addition of extra methyl groups. This increase in permeabilities has been subscribed to an increase in the number of large free spaces. The synthetic polymer with the largest measured permeabilities is poly(1-trimethylsilylpropyne). This polymer possesses a carbon dioxide permeability of 28,000 barrer and a nitrogen permeability of 4970 barrer. These very large permeabilities are associated with a very large fractional free volume. These permeabilities tend to decrease with time due to slow crystallisation of the polymer. This effect can be counteracted by the addition of certain additives. Other polyacetylenes give lower,
Gas transport properties are affected by the method by which the membrane is constructed. Yilmaz and co-workers have investigated the effect on gas transport properties by altering the preparation of a polycarbonate membrane [101]. By altering the concentration of polymer in the casting solvent, slight changes to the permeability are observed. Changes of a similar magnitude are also observed when dichloromethane is used instead of chloroform as the casting solvent. Other preparation variables investigated include drying time, and annealing time. Another study by Tsujita and co-workers has examined the effect of thermal and pressure conditioning on the gas transport properties of polycarbonates [102]. The authors found that heating the polycarbonate above Tg , and then quenching the lm would increase the CO2 sorption. As the heating was increased, the CO2 sorption capacity of the membranes likewise increased. This increased sorption was attributed to an increase in CH . Koros and co-workers have also investigated the carbon dioxide permeability of various polycarbonates at high pressures [103]. For these reasons, it is best to compare membranes that have been prepared with identical methodology. Materials for effective separation of gases can follow one of two overall strategies; increasing the rate of diffusion of carbon dioxide through the polymeric structure and increasing the solubility of carbon dioxide in the membrane. Unfortunately, there is frequently a trade-off between selectivity and permeability. The introduction of mixed-matrix membranes may allow superior performance; however, there is considerably less scope for the rational design of these membranes. The rate at which gases diffuse through a polymeric matrix depends on the amount and distribution of the free volume within the polymer. As the gas molecules jump from one transient cavity to another, manipulation of the polymer structure can alter the barrier between cavities allowing carbon dioxide to diffuse through the polymer structure signicantly faster than nitrogen. Further, to the synthetic strategy described earlier, changes in the polymer packing can signicantly alter the permeabilities in a number of ways: Incorporation of bulky side groups into the polymers backbone tends to lead to an increase in the permeabilities, with a corresponding loss in selectivity. However, in many cases, the loss of selectivity is slight compared with the increase in carbon dioxide permeability.
Fig. 7. Examples of high free fractional volume polymers.
but still substantial permeabilities. Another polymer with an extremely large fractional free volume, and hence permeabilities is poly(dimethylsiloxane) which possesses a carbon dioxide and nitrogen permeabilities of 4550 and 351 barrer, respectively. A recent communication by Budd et al. expands the eld of high fractional free volume gas separation membranes [105]. Two aromatic rigid yet twisted polymers (denoted as polymers of intrinsic microporosity) have been synthesised and their permeabilities measured. The carbon dioxide permeabilities range from 1100 to 2300 barrer, while the nitrogen permeabilities range from 92 to 42 barrer. Unlike other high fractional free volume polymers, these polymers also incorporated reasonable solubility selectivities. The structure of these polymers is displayed in Fig. 7. Polyaniline has been extensively studied in the literature [3942]. Polyaniline which had been doped with HCl, dedoped with ammonia and nally redoped with HCl have been reported to give very high selectivities [39,40]. For example, an ideal selectivity for CO2 /N2 of 1560 has been reported [39]. Subsequent studies, have found considerably lower selectivities, with Hellgardt reporting a CO2 /N2 ideal selectivity of only 17 [42]. Because of the low CO2 permeability of polyaniline membranes (Hellgardt, for example, reports a CO2 permeability of approximately 0.1 barrer [42]), it is unlikely that they will be useful for the capture of carbon dioxide. Yoshino et al. have examined a number of high molecular weight branched poly(ethylene oxide)-based polymers [56]. These polymers were synthesised by using a combination of various monomers; ethylene oxide (EO), 2-(2methoxyethoxy)ethyl glycidyl ether (EM) and allylglycidyl ether (AGE). These polymers give very good combinations of carbon dioxide permeabilities and selectivities, with one example possessing a carbon dioxide permeability of 773 barrer and a carbon dioxide/nitrogen selectivity of 46. Because these gas transport properties of these materials were tested at different pressures and temperatures to the majority of the gas permeabil-
ity literature, a direct comparison of gas transport properties is difcult. A number of polymers types have shown good gas transport properties and considerable scope for structural variations. The following describes the main polymer types which have been studied as CO2 separation membranes. 2.2.1. Polyarylates A large number of polyarylates have been synthesised and their gas transport properties studied. The most common synthetic route involves reaction of a diol, such as bisphenol A, with an acid chloride to afford the desired polyarylate. This reaction can be performed under a variety of conditions such as interfacial or a stepwise polycondensation. The structure of a common polyarylate is displayed in Fig. 8. The oxygen/nitrogen separation properties of polyarylates have been reviewed by Paul and Pixton [106]. The carbon dioxide permeabilities and carbon dioxide/nitrogen selectivities for a number of polyarylates is graphed in Fig. 9. Most polyarylates possess carbon dioxide permeability less than 25 barrer; however, a small number possess permeabilities as high as 85. The sterically bulky polyarylate, TBHFBPA/tBIA, exhibits the highest carbon dioxide and carbon dioxide/nitrogen selectivity of 19, the structure of which is displayed in Fig. 10. 2.2.2. Polycarbonates A number of polycarbonates have been synthesised and their carbon dioxide/nitrogen gas transport properties studied. Poly-
Fig. 8. PA.
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Fig. 9. Carbon dioxide permeability vs. selectivity for polyarylates.
carbonates are generally synthesised by reaction between a diol and phosgene under a variety of conditions. Like many polymeric materials used in the synthesis of gas separation membrane materials, the ready availability of structural variants of bisphenol A has led to a large number of different polymers. Most polycarbonates tend to have a carbon dioxide permeability of under 40 barrers, and selectivities range from 15 to over 25. One notable exception to this is the polycarbonate TMHFPC, which possess a carbon dioxide permeability of 111 and a carbon dioxide/nitrogen selectivity of 15.0. The structure of this polymer is displayed in Fig. 11. The carbon dioxide permeability and carbon dioxide/nitrogen selectivities for a number of polycarbonates are graphed in Fig. 12. 2.2.3. Polyimides Polyimides combine excellent thermal and chemical stability with a very wide range of carbon dioxide permeabilities. Some polyimides, particularly those incorporating the group 6FDA possess very high carbon dioxide permeability. An extensive review of the gas separation properties of polyimides was published in 1996 [13].
Polyimides are generally synthesised by the reaction of a diamine with a diahydride in an aprotic solvent to form a polyamic acid. This polymer then undergoes a polycondensation reaction (either thermally or chemically) to form the desired polyimide. An example of the synthesis of the polyimide 6FDApPDA is displayed in Scheme 1. A number of different diahydrides have been used in the synthesis of polyimides for gas separations; these include PMDA, 6FDA and BTDA. The chemical structures of these dianhydrides is displayed in Fig. 13. While most polyimides are synthesised using either PMDA, BPDA or 6FDA as the dianhydride, a number of authors have synthesised novel dianhydrides for the use in the formation of novel polyimides [66,107]. The structures of these starting materials are displayed in Fig. 14. These dianhydrides were then reacted with a range of diamines to give a number of polyimides. The polyimide, PITMMPA, has been observed to give extremely high permeabilities. This result is unsurprising given the large steric bulky nature of the polymer (Fig. 15). Polyimides incorporating the group 6FDA have been the object of much research, as they tend to combine both high selectivities and high permeabilities. Three reasons are commonly given for this behaviour: (a) the CF3 groups considerably increase the stiffness of the chain, allowing the membrane to more effectively separate molecules on the basis of steric bulk; (b) effective chain packing is reduced by the large CF3 groups which leads to an increase in the permeability; (c) the formation of charge-transfer complexes is reduced, which in turn reduces the likelihood of effective chain packing [9,108].
Fig. 10. TBHFBPA/tBIA.
Fig. 11. TMHFPC.
Fig. 12. Carbon dioxide permeability vs. selectivity for polycarbonates.
11
Scheme 1. Synthesis of 6FDApPDA.
Another target of considerable research is the commercial polyimide, Matrimid 5218, which is shown in Fig. 16. Matrimid has been functionalised by brominations. Bromination tended to increase both the carbon dioxide and nitrogen permeabilities, leading to only a small decrease in the carbon dioxide/nitrogen selectivity [109]. A study on the effect of cross-linking Matrimid 5218 is discussed in Section 2.4. Fig. 17 displays the carbon dioxide permeability and carbon dioxide/nitrogen selectivities of a variety of polyimides. 2.2.4. Polypyrrolones Polypyrrolones are structurally similar to polyimides; however, they are considerably more rigid. Polypyrrolones are of interest because of their high thermal and chemical resistance, which can be greater than that of similar polyimides. However, despite this, the number of different polypyrrolones which have been studied is quite limited. The structures of these polymers are displayed in Fig. 18. Because of their high rigidity, it has been suggested that polypyrrolones can act as a molecular sieve.
For this reason, a signicant volume of the literature covers copolypyrrolones and copoly(imides pyrrolone), as varying the proportion of the mers can vary the rigidity. Polypyrrolones are generally synthesised by reaction of dianhydride and a tetraamine functionalised monomer. The synthesis of the polypyrrolone 6FDATAB is displayed in Scheme 2. The presence of the tetraamine groups required for reaction signicantly limits the possible structural variations. Zimmerman and Koros have published a series of papers investigating copolymers of 6FDA/PMDATAD [79,80]. The results of these are discussed more fully in the copolymer section. Walker and Koros have investigated a polypyrrolone 6FDATADPO and compared it to a number of polymers [82]. Zimmerman and Koros have performed an investigation into a copolypyrrolone, 6FDA/PMDATAB, the structure of which is displayed in Fig. 19 [79,80]. As the proportion of PMDA increases, the carbon dioxide permeability decreases and the selectivity increases. The temperature dependence of these copolypyrrolones has also been studied [80].
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Fig. 16. Matrimid 5218.
Fig. 17. Carbon dioxide permeability vs. selectivity for polyimides.
Fig. 13. Common dianhydrides used in the synthesis of polyimides.
Fig. 18. Polypyrrolone structures.
Fig. 14. Catechol-based dianhydrides.
Fig. 15. PITMMPA.
Scheme 2. Synthesis of 6FDATAB.
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Fig. 19. 6FDA/PMDATAB.
2.2.5. Polysulfones Considerably amounts of research have been performed on the gas transport properties of polysulfones, because of their reasonable performance and low cost. Polysulfones are already used in industrial gas separation processes [6]. Polysulfones are generally synthesised by a condensation reaction between a bisphenol and a dihalogenated diphenylsulfone. The most extensively studied polysulfone is PSF, formed using bisphenol A. Two routes for the synthesis of PSF are displayed in Scheme 3. Most other polysulfones are structurally related to this polymer. An extensive study of the gas transport properties of PSF has been performed by Paul and co-workers [54]. By substitution of bisphenol A with a different diol, large numbers of PSF derivatives have been synthesised. These display a wide range of carbon dioxide permeabilities and selectivities. More exotic polysulfones have also been examined. Pixton and Paul have investigated the transport of different adamantanebased polysulfone membranes [88]. Aitken and Paul have likewise examined naphthalene-based polysulfone membranes [91]. The structures of these polymers are displayed in Figs. 20 and 21.
Some polysulfones have been functionalised by a bromination [110]. This increases the reactivity of the polymer, leading to the potential for more structural variation. Guiver and coworkers have abstracted the bromine atom with butyl lithium and subsequently performed a reaction with iodotrimethylsilane [85]. Bonfanti et al. have further reacted the polymers with a series of acetylenes utilising a PdII /CuI catalyst (Scheme 4) [87]. A number of different polymers were successfully synthesised with different degrees of bromination and alkylation. Both the bromination and alkylation steps were not carried out to completion, ensuring that the nal products were composed of a mixture of unreacted monomer, brominated monomer and alkylated monomer. A number of polysulfones have been modied by reaction with butyl-lithium followed by addition of a pendent group [8386]. The reaction site on the polymer can be altered by using a brominated polysulfone as a precursor. Using this technique a number of novel polysulfones structurally related to PSF (Fig. 22), HFPSF (Fig. 23), PPSF (Fig. 24) and TMPSF (Fig. 25)
Fig. 20. Adamantane-based polysulfone membranes.
Fig. 21. Naphthalene-based polysulfone membranes.
Fig. 22. Novel polysulfones-based off PSF.
14
Scheme 3. Synthesis of PSF.
have been synthesised and their gas transport properties examined. An NMR study of some polysulfones modied by addition of a trimethylsilyl group found a decrease in chain mobility when the Me3 Si group was ortho to the sulfone group through the ether linkage [111]. Fig. 26 displays the carbon dioxide permeability and carbon dioxide/nitrogen selectivity for a variety of polysulfones. 2.2.6. Copolymers and polymer blends Copolymers offer the potential to ne tune permeabilities and reduce the costs of polymer synthesis. A copolymer will tend to have permeabilities which are intermediate compared with the homopolymers which make it up. Likewise an expensive and effective polymer can be signicantly reduced price
by the formation of a copolymer which incorporates cheaper monomers. A series of copolyimides formed from reaction of NTDA with a mixture of sulfonated and non-sulfonated diamines was synthesised by Espuche and co-workers [63]. The structure of these copolyimides is displayed in Fig. 27. As the proportion of sulfonated groups increases, the carbon dioxide permeability drops dramatically. The CO2 /N2 gas separation properties of a large series of poly(ethylene oxide) segmented copolymers with polyurethanes, polyamides and polyimides have been investigated by Okamoto and co-workers [112]. These copolymers generally gave both high selectivities and a high CO2 permeability, likely due to the high solubility of carbon dioxide into the
15
Scheme 4. Synthesis of alkynylated PSF.
poly(ethylene oxide) segments. Of particular note is the polymer PMDA-pDDS/PEO4(80) (Fig. 28) which exhibits a CO2 permeability of 238 barrer and a CO2 /N2 selectivity of 49. This combination of both high selectivities and permeabilities may be related to the low pressures used during the determination of the gas transport properties. Chung and co-workers have synthesised and determined the gas transport properties of a series of copolyimides incorporating the 6FDAdurene and 6FDApPDA subunits [65]. As the proportion of 6FDApPDA increases, a decrease in the permeabilities is observed. The increase in permeabilities for certain copolyimides is greater than expected from the addition rule of the semi-logarithmic equation. This unexpected increase is due to a greater increase in the solubility coefcients than antcipitated. Similarly 6FDA copolyimides have been synthesised [61,113]. Dense lms of 6FDAdurene and 6FDAdurene/mPDA (50:50) have also been reacted with N,N-dimethylaminoethyleneamine in hexane to perform an amidation on the group ring [58]. The reaction is displayed in Scheme 5. By increasing the reaction time, the degree of amidation was also increased. A decrease in the permeabilities was observed with an increase in the amount of amidation. Similarly, a series of three component polyimides have been synthesised and their gas permeabilities tested [68]. 6FDA has
been reacted with various ratios of two diamines, FDA and HFBAPP, to give a number of copolyimides. Pure 6FDAFDA has greater carbon dioxide and nitrogen permeabilities than pure 6FDAHFBAPP. As the weight fraction of FDA increases, the permeabilities increase. Copolysulfones incorporating both bisphenol A and 1,1-bi2-naphthol have had their gas transport properties studied [114]. As the naphthol concentration increases, both the carbon dioxide and nitrogen permeabilities decrease. A copoly(imide pyrrolone), 6FDATAB/DAM has been examined by Burns and Koros [115]. The structure of this copolymer is displayed in Fig. 29. Increasing the proportion of DAM leads to an increase in the permeability and a decrease in the selectivity. The oxygen/nitrogen separation properties of 6FDATAB and the copolymer 6FDA/PMDATAB has been examined by Zimmerman and Koros [78]. While, the authors do not investigate carbon dioxide transport, the paper contains an interesting discussion on the relationship between entropy and permeability. The polypyrrolones studied in the paper, are extremely rigid, and function more like molecular sieves than polymeric membranes. Sakellaropoulos and co-workers have investigated the gas transport properties of a series of polysulfonepolyimide polymer blends [116,117]. The authors found that the effect of
16
Fig. 23. Novel polysulfones-based off HFPSF.
increasing the proportion of polyimide on the transport properties of gases which do not interact signicantly with the polymer matrix can be described by a simple relationship. The permeability of carbon dioxide, however, is lower for the polymer blends than what would be expected if it follows a similar relationship. The authors suggest that this could be due to interactions between the carbon dioxide and polyimide or densication and consolidation of the membrane induced by the presence of high pressure carbon dioxide. Okamoto and co-workers have investigated a series of star polymers incorporating a 6FDA-based polyimide core and poly(ethylene oxide) arms [118]. Tris(4-aminophenyl)amine was reacted with 6FDA to give a mixture of hyper-branched polyimide cores. By varying the ratio of 6FDA to tris(4aminophenyl)amine the composition of the polyimide cores
Fig. 24. PPSF and novel polysulfones-based off PPSF.
could be altered. These cores were then reacted with a variety of poly(ethylene oxide) chains. These poly(ethylene oxide) molecules varied in both molecular weight (2000, 2840 or 5000) and terminal groups (amino or hydroxyl). The membranes could then be doped with a variety of ions. A series of poly(imide siloxane) copolymers have been synthesised by Smaihi et al. and their gas transport properties determined [119]. The synthesis of these network membranes is displayed in Scheme 6. The amic acid precursors were cast and then heat to form both the imide and siloxane bonds. The nitrogen and carbon dioxide gas transport properties of the hybrid membranes was tested at both 90 and 190 C. Marand and co-workers have likewise investigated the gas permentation properties of thermally annealed polyimide-organosilicate hybrid membranes [59]. Silica-polyimide membranes have likewise been prepared by Morooka and co-workers [120]. The membranes were synthesised by mixing a polyamic acid with a mixture of tetraethyl orthosilicate, 3-glycidyloxypropyltrimethoxysiland and a coupling agent. The solution was then cast onto alumina support tubes which were then heated at 350 C to form the networked membrane. The presence of the silica increased the carbon dioxide permeability at the cost of selectivity. Nanocomposite membranes incorporating polyacetylenes have also been synthesised by Peinemann and co-workers [121].
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Fig. 25. Novel polysulfones-based off TMPSF.
2.3. Pressure/temperature effects The relationship between temperature and gas transport properties can be expressed with the following equations: P = P0 exp S = S0 exp EP RT Hs RT , D = D0 exp ED RT ,
Fig. 26. Carbon dioxide permeability vs. selectivity for polysulfones.
where P0 , D0 and S0 are the initial conditions, EP and ED the activation energies for permeation and diffusion, respectively
Fig. 27. NTDABDSA/ODA.
Fig. 28. PMDApDDS/PEO4(80).
Fig. 29. 6FDATAB/DAM.
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Scheme 5. Reaction of N,N-dimethylaminoethyleneamine and 6FDAdurene.
and Hs is the heat of sorption. This implies that increasing the temperature should lead to an increase in the permeability and a decrease in the selectivity of a membrane. Lin and Freeman have investigated the gas transport properties of poly(ethylene oxide) for a large number of gases at different temperatures [55]. The permeabilities of both carbon dioxide and nitrogen were measured at 25, 35 and 45 C. The permeabilities of both gases increased dramatically upon heating; however, the CO2 /N2 selectivity suffered a signicant loss. The effect of changing the upstream pressure was also investigated. The permeability of carbon dioxide increases with pressure,
indicating plasticisation of the membrane, whereas nitrogen permeability decreases slightly with increased pressure, as expected from the dual-mode sorption model. The authors applied the following empirical model to these results: PA = PA (1 + m p) = PA,0 (1 + mp2 ) where PA,0 is the permeability at an innitely small pressure difference, m an adjustable constant, p2 the upstream pressure and p is the pressure difference across the membrane. From this they determine that for CO2 PA,0 = 12 1.0 barrer and m = 34 10 atm1 , whereas NO2 PA,0 = 0.25 0.02 barrer and m = 10 7 atm1 . Stern and co-workers have investigated the gas transport properties of a series of 6FDApolyimide membranes [72]. Of particular interest, an empirical relationship between pressure and permeability was developed: log P = n + m p where n and m are the constants. By tting experimental data to this equation, n and m have been determined (Table 4). Villaluenga and Tabe-Mohammadi have examined the effect of pressure variations on both glassy and rubbery polymers [122]. The effect of altering the pressure was much more signicant when the rubbery polymer was examined, whereas the glassy polymer was unaffected by pressure changes. However,
Table 4 Pressure dependence of permeabilities Polymer CO2 n 6FDAmPDA 6FDAmMPDA 6FDADATr 6FDADBTF 0.986 1.512 1.700 1.412 m (105 ) 70.71 55.13 71.42 76.97 N2 n 0.427 0.101 0.344 0.098 m (105 ) 10.19 15.15 22.95 32.61
Scheme 6. Synthesis of poly(imide siloxane) copolymers.
Data from Ref. [72].
19
as the authors did not use a highly condensable gas, such as carbon dioxide, the glassy polymers are expected to be less susceptible to pressures changes. Koros and co-workers have investigated the effect of carbon dioxide plasticisation in a small number of polyimide membranes [123]. They investigated the effects of increasing the temperature on the gas transport properties of two polyimides: 6FDADAF and 6FDAIPDA [73]. Costello and Koros have similarly examined 6FDA6FpDA and 6FDA6FmDA over a large temperature range (35325 C) and have suggested that 6FDA6FpDA would be a candidate for incorporation into a high temperature application. Koros and co-workers have performed an in-depth study of the temperature effects on the gas transport properties of the polypyrrolone 6FDATADPO [124]. The 6FDATADPO membranes were heated from 35 to 200 C. Both the preexponential factor P0 and the activation energy EP have been determined. 6FDATADPO possesses a P0 of 5.0 101 and 2.0 102 barrers for carbon dioxide and nitrogen, respectively. Above 150 C, the P0 is better expressed as 9.3 102 and 5.0 103 barrers. The activation energies, EP are listed as 0.28 and 3.1 kcal mol1 for carbon dioxide and nitrogen, respectively. Above 150 C, the activation energies are 2.7 and 5.8 kcal mol1 . 2.4. Cross-linking Cross-linking offers the potential to improve the mechanical and thermal properties of a membrane. Koros and Mahajan have suggested that cross-linking can be used to increase membrane stability in the presence of aggressive feed gases and to simultaneously reduce plasticisation of the membrane [14]. Copolymers of poly(ethylene oxide-co-epichlorohydrin) have been cross-linked with various concentrations of Kbismuththiol [125]. The effect of increasing the proportion of cross-linking agent is tabulated in Table 5. The effect of increasing the proportion of ethylene oxide on the carbon dioxidenitrogen selectivity was also examined (K-bismuththiol
Table 5 Effect on increasing proportion of K-bismuththiol on gas transport properties of poly(ethylene oxide-co-epichlorohydrin) Cross-linking agent 1.1 g/100 g polymer 2 g/100 g polymer 5 g/100 g polymer CO2 permeability 15.0 14.9 16.1 N2 permeability 2.3 1.0 0.5 CO2 /N2 selectivity 6.5 15 32
Permeabilities measured at 25 C. Data from Ref. [125].
was kept constant at 5%). The selectivity increases with the ethylene oxide concentration, peaking at 93 mol%. At this concentration the selectivity is 63.0. Increasing ethylene oxide concentration causes a dramatic decrease in the selectivity. Hirayama et al. have investigated the effects of cross-linking poly(ethylene oxide) on the carbon dioxide and nitrogen gas transport properties [126]. Methacrylate terminated monomers incorporating poly(ethylene oxide) of various lengths (Fig. 30) were photo polymerised. All of the polymers gave good CO2 /N2 selectivities, and most exhibited large CO2 permeabilities at temperatures up to 100 C. A patent published by Kita et al. has demonstrated excellent CO2 /N2 properties for cross-linked various poly(ethylene oxide) polymers [127]. These polymers were prepared by the polymerization of various oxirane compounds. Cross-linking was achieved via a variety of methods, including reaction with peroxides, azo containing compounds and hydrosilylation reactions. Recently a large volume of research on cross-linked poly(ethylene oxide) has been published by Freeman and co-workers [128,129]. The authors have also published a useful paper on material selection for solubility selective polymers which possess good carbon dioxide permeabilities while still possessing excellent carbon dioxide/light gas selectivity [130]. An unsuccessful attempt at improving gas transport properties by cross-linking a polyarylate has been performed by Wright and Paul [131]. The authors synthesised a copolyary-
Fig. 30. Monomers used by Hirayama et al. [126].
20
Fig. 31. FBP/XTA-C110/tBIA.
late, FBP/XTA-C110/tBIA, and exposed it to 350 C to induce cross-linking. The copolyarylate is displayed in Fig. 31. Upon heating to 350 C, the cyclobutene group can cause cross-linking by linear addition and cycloaddition. Thermal decomposition of the polymer was observed during the cross-linking stage. Upon heating, a small increase in the permeability of the copolyarylate was observed (CO2 permeability increases from 33 to 37 barrer, N2 permeability increases from 2.17 to 2.35 barrer). The authors suggest that changes in the gas transport properties are due to degradation reactions. Rezac et al. have blended 6FDAIPDA with a diacetylene containing oligomer 6FDADIA [132]. Cross-linking can then be achieved by heating the membrane to 340 C under vacuum. Cross-linking decreased the solubility of the membranes in dichloromethane and N-methylpyrrolidone dramatically. Crosslinking the polymers did not signicantly alter the gas permeabilities; however, increasing the proportion of 6FDADIA did lower both the carbon dioxide and nitrogen permeabilities. Nakagawa and co-workers have incorporated a photosensitiser into a polyimide membrane and irradiated with UV light to induce cross-linking [133]. The use of diamines to cross-link polyimides was patented in 1991 [134]. The use of diamines to cross-link polyimides has been a topic of considerable interest in the literature since 2001. Chung and co-workers have cross-linked 6FDAdurene and Matrimid 5218 dense membranes by soaking the membranes in a solution of p-xylenediamine in methanol [57,64]. The methanol causes the membrane to swell, while the p-xylenediamine reacts with two carbonyl groups cross-linking the polyimide. Exposure of 6FDAdurene to the p-xylenediamine/methanol solution quickly causes a reduction in the permeabilities (the magnitude of the reduction depends on the exposure time). The carbon dioxide/nitrogen selectivity is also observed to decrease upon exposure to the solution. When other gas systems (such as He/N2 and O2 /N2 ) were investigated, an increase in the selectivities was observed. Matrimid 5218 gives similar, although slower, results for carbon dioxide/nitrogen separations, however, the effects of cross-linking on gas permeabilities did not begin to become signicant until after a week of exposure to the pxylenediamine/methanol solution. The change in the Matrimid 5218 membranes carbon dioxide permeability over exposure time is graphed in Fig. 32. Membranes formed from the polyimide 6FDAdurene can be cross-linked by reaction with a diaminobutane dendrimer in methanol solution [135]. Longer reaction times led to a larger degree of cross-linking. As the dendrimer generation number increased, the speed at which cross-linking occurred decreased,
possibly due to reduced diffusion of the cross-linking agent into the membrane. Both the carbon dioxide and nitrogen permeabilities decreased signicantly with increased cross-linking. Similar work has been performed on 6FDAdurene and a PAMAM dendrimer [136]. Increased cross-linking generally leads to increase in the carbon dioxide/nitrogen selectivities at the cost of carbon dioxide permeability. Koros and co-workers have synthesised carboxylic containing polyimide membranes which can then be cross-linked by either a transesterication reaction or reaction with a metal ion [123,137139]. These membranes have been investigated for their usage in CO2 /natural gas separations; however, it is likely that they will give similar results for CO2 /N2 separations. A patent by Hayes has investigated photochemical crosslinking of copolyimides which include a benzophenone functional group [140]. Improvements in the selectivities for some gas pairs were noted upon irradiation induced cross-linking. The cross-linking is thought to occur between the benzophenone moiety and an alkyl substitute on the diamine section of the polyimide. Won et al. have investigated the effects of surface modication of polyimide (Matrimid 5218) and polysulfone (PSF) membranes by an ion beam [141]. In both cases, there was a signicant drop in the CO2 permeability, with a corresponding large increase in the CO2 /N2 selectivity. 2.5. Mixed-matrix membranes Mixed-matrix membranes refer the incorporation of solid particles within a membrane. Generally the presence of particles can
Fig. 32. Carbon dioxide permeability vs. p-xylenediamine/methanol solution exposure time.
21
have three effects on the permeabilities; they can act as molecular sieves altering the permeabilities, they can disrupt the polymeric structure increasing permeabilities and they can act as barrier reducing permeabilities. Generally the literature has focused on the incorporation of molecular sieves into a polymer matrix. Often these molecular sieves possess superior gas transport properties, but have signicant problems with their processability. A number of articles providing an overview of mixed-matrix membranes have been previously published [142,143]. The Maxwell equation can be used to model the gas transport properties of mixed-matrix membranes [142]. The behaviour of gases within a mixed-matrix will vary depending on the spatial relationship of the particles within the matrix. If a gas molecule can make a continuous path through the particles without significant transport through the polymeric material, it would exhibit different behaviour to a gas molecule which is forced to take a discontinuous path through both the polymeric material and the solid particles. If the mixed-matrix material acts as in a continuous fashion then the permeability can be modelled as Peff = P1 1 + P2 2 where Pn is the permeability and n is the volume fraction of component n. Whereas, if the material acts in a discontinuous fashion, then the permeability can be described as Peff = P1 P2 1 P2 + 2 P1 Pd + 2Pc 2d (Pc Pd ) Pd + 2Pc + d (Pc Pd )
Table 6 Theoretical and experimental CO2 permeabilities of mixed-matrix membranes Carbon dioxide permeability (barrer) Bruggeman model Matrimid 5218 17% CMS 19% CMS 33% CMS 36% CMS Ultem 1000 16% CMS 20% CMS 35% CMS Maxwell model Modied Maxwell model 11.0 11.2 12.1 12.3 Experimental
13.1 13.5 17.0 17.8 2.33 2.59 4.23
13.0 13.3 16.5 17.2 2.21 2.40 3.44
10.3 10.6 11.5 12.6 2.51 2.90 4.48
Data from Ref. [144].
For a dilute suspension of spheres in a matrix: Peff = Pc
where Pd and Pc refer to the permeabilities of the dispersed and continuous phase, respectively. In principle, a mixed-matrix membrane will exhibit discontinuous behaviour when the concentration of solid particles is low, and will tend towards continuous behaviour when the concentration of the solid particles is high. Effective medium theory (EMT) has likewise been used to model mixed-matrix membranes [142]. Koros and co-workers have compared theoretical permeabilities with experimental derived permeabilities of Matrimid 5218 and Ultem 1000 mixed with carbon molecular sieves (CMS) [144]. The authors investigated two models, Maxwell and Bruggeman (Table 6). The Bruggeman model uses the following equation when examining a random dispersion of spherical particles: (Peff /Pc ) (Pd /Pc ) 1 (Pd /Pc ) Peff Pc
1/3
tion of particles, as well as the formation of spaces between the solid particle and the polymeric material. This can allow the gases to ow non-selectively around the solid particles. Koros has suggested experimental procedures to minimise these issues; sonication and decantation of smaller solid particles can increase the viscosity of the casting solution reducing both aggregation, sedimentation, and priming the particles with small amounts of the polymer can increase polymerparticle interactions, as can reducing the rate of evaporation of the casting solution [145]. Thompson et al. have tried to avoid these problems by synthesising zeolite containing polymeric hybrid materials using covalent bonding of the zeolite to the polymer matrix [146]. Chung et al. have formed mixed-matrix membranes from Matrimid 5218 and a benzylamine-modied fullerene [147]. Fig. 33 displays the carbon dioxide and nitrogen permeabilities versus increased fullerene content. Addition of the fullerene appears to lower the permeabilities of all of the examined gases. The authors suggest that the fullerene is causing rigidication of the polymer matrix, leading to a decrease in the diffusion coefcient. Koros and co-workers have investigated a number of different polymeric membranes (polycarbonate, polysulfones and 6FDA polyimides) formed on silicon dioxide impregnated ceramic
= 1 d
Considerable differences between the calculated and experimental permeabilities were observed. This was particular in the case of Matrimid 5218. The authors suggested that this was due to rigidication of the polymer where it was in close proximity to a CMS particle. The authors used a modied version of the Maxwell equation to account for this and obtained a much close correlation with the experimental results (Table 6). Three potential problems with the formation of effective mixed-matrix membranes are the aggregation and sedimenta-
Fig. 33. Effect of increased proportion of benzylamine modied fullerene in Matrimid 5218 mixed-matrix membranes gas transport properties.
22
substrates [148]. The authors observed an increase in the selectivities compared with dense membranes of the polymers, as well an increase in the permeabilities. A series of mixed-matrix membranes incorporating powdered polypyrrole and polycarbonate have been synthesised and their gas transport properties determined by Yilmaz and coworkers [149]. Both the nitrogen and carbon dioxide permeabilities increase as the concentration of polypyrrole is increased. Other mixed-matrix membranes using polymeric particles have been examined [60]. Interestingly, when PMDAODA was mixed with poly(styrene-co-4-vinylprydine) nanoparticles in certain proportions an increase in both the carbon dioxide permeability and carbon dioxide/nitrogen selectivity was observed [60]. Spontak and co-workers have formed mixed-matrix membranes from cross-linked poly(ethylene oxide) and various nanoparticles [150,151]. While these membranes were examined primarily for their CO2 /H2 separation performance, some CO2 /N2 data was collected. 2.6. Asymmetric membranes For membranes to be used in practical applications, it is necessary for them to be constructed into a useful morphology. An extensive review of membrane structures is beyond the scope of this review. What follows is a brief introduction into this eld. Most studies on the gas transport properties of polymers are performed on dense homogeneous membranes. Dense membranes are generally synthesised by casting a solution of solvent and polymer onto a at surface, and then allowing the solvent to evaporate. As such, their permeability has a close relationship to the intrinsic permeability of the polymer. These studies allow the efciency of a material to be evaluated, as far as experimental margins of error permit. However, the construction of a gas separation module requires a more complex membrane structure to be used. Dense membranes tend to be signicantly thicker than the selective layer of asymmetric membranes. This leads to dense membranes possessing considerably lower gas uxes than alternative membrane structures. Ultra thin membranes have also be constructed by more exotic techniques, such as collision of hyperthermal protons with absorbed organic precursors [152].
Fig. 34. Structure of a typical asymmetric membrane (from Ref. [155]).
Conceptually, the simplest type of asymmetric membrane is one formed via a Loeb-Sourirajan phase separation process. This gives a membrane with two components: a defect free selection layer (similar to that found on a dense lm membrane) and a porous support layer (Fig. 34). These membranes can be manufactured as either at sheets or hollow bres (Fig. 35). For an asymmetric membrane to have similar selectivities to the intrinsic selectivity of the material, it is important that the gas ux of the substructure be considerably greater than the ux through the selective layer [153]. Flat sheet asymmetric membranes have been constructed from a number of different polymeric materials, including polysulfones [154,155], polyetherimide [156,157] and polyimides [158]. Hollow bre membranes have been constructed using a number of different polymeric materials, including polysulfones [159162], polyethersulfones [163], polyphenylene oxide [164], polyetherimide [165], polyimides [166168], polycarbonates, polyimidepoly(ethylene oxide) copolymers[169] and polymer blends [170]. Recent patents include useful details about the synthesis of various asymmetric membranes [171,172]. Lin and Chung have investigated the effect of aging on the performance of hollow bre membranes constructed with 6FDAdurene [173]. Khulbe et al. have carried out atomic force microscopy and contact angle goniometery studies on a polyethersulfonepolyimide blend hollow bre membrane [174].
Fig. 35. SEM pictures of a hollow bre membrane (from Ref. [175]).
23
A number of recent studies have been carried out on the effect of preparation variables and aging of hollow bre membranes [175178]. Chung and co-workers have constructed dual-layer hollow bre membranes using polyimide and a poly(ether sulfone) to construct each layer [179]. The membrane was then cross-linked by soaking the hollow bres in a solution of p-xylenediamine in methanol. The carbon dioxide/nitrogen selectivity of a hollow bre membrane system consisting of cardo polyimides has been dramatically increased (from 35 to 81) by the incorporation of an inner layer consisting of a zero-generation polyamidoamine dendrimer. The carbon dioxide gas ux, does however, drop by almost 50% [36]. The effect of lling agents on the structural, mechanical and gas transport properties of silicon coated polysulfone hollow bre membranes has been investigated by Shilton and coworkers [180]. Carbon black (CB), vapour grown carbon bres (VGCF) and TiO2 were all trialled as llers. The concentration of VGCF and TiO2 was 5%, whereas CB was trialled at 2, 5 and 10% (w/w). The introduction of VGCFs caused a reduction in the CO2 permeability and an increase in the N2 permeability, leading to a change in selectivity from 42 to 14. TiO2 also induced an increase in the N2 permeability; however, the CO2 permeability was essentially unchanged. The new selectivity was 28. The introduction of 2% CB led to only minor changes for the permeability of both gases, whereas 5% CB led to a small increase in the N2 permeability and a small decrease in the CO2 permeability. 10% CB reversed this trend and led to a selectivity of 33. With all llers, the gas transport properties for the CO2 /N2 gas pairs were worse than polysulfone. The addition of the llers (with the exception of VGCF) did lead to an increase in the bursting pressures of the membranes. The authors postulated that the llers increased the fractional free volume; however, the carboncontaining llers interacted with the carbon dioxide leading to a reduction in its permeability. Another type of asymmetric membrane is the composite membrane. Composite membranes utilise two or more different polymeric materials in their construction. Often an expensive selective layer is combined with a cheaper layer which provides structural support. Frequently a three layer system is synthesised by the addition of a protective layer above the selective layer. Composite membranes can take a number of different morphologies, such as hollow bre. Pinnau and co-workers have published an interesting discussion of composite membranes [181]. A number of composite membranes have been constructed from a number of different polymeric materials; including poly(ethylene oxide) containing polyimides [169], sulfonated poly(phenylene oxide) [75], polyimides [182,183] and polysulfones. Composite membranes can be constructed by a variety of techniques including dip coating [184] and chemical vapour deposition [185]. 3. Conclusions Geosquestration of carbon dioxide is an emerging technology used to reduce the impact of fossil fuel combustion. Chemists
can play an important role in the development of this technology, one such role is the development of novel polymeric materials for the separation of carbon dioxide from nitrogen in power plant gas ues. While this review concentrates on ue gas CO2 /N2 separation, there are a number of different locations where membranes can play a signicant role. In addition to the power generation industry, there are a number of different point sources which produce large CO2 emissions (steel foundries, etc). N2 /O2 separation membranes can be used to create oxygen enriched air, which can be used in combustion, to get concentrated CO2 ue gases. CO2 can also be separated from fuel gases leading to lower CO2 emissions. The carbon dioxide and nitrogen gas transport properties of a number of polymeric membranes have been discussed. A number of different classes of polymers have been surveyed for their utility as materials for effective gas separation membranes. Some types of polymers, such as polycarbonates, polysulfones and polyimides, combine good performance while possessing considerable scope for structural variation. One possible strategy towards the synthesis of high performance gas separation membranes is the construction of polymers consisting of both hard and soft sections. While many polymers have been described here, the class of polymer with the largest volume of research are polyimides, particularly polyimides which incorporate 6FDA. This is due to their gas transport properties, good physical properties, potential structural variations and ease of membrane formation. It is expected that this trend towards increased research on polyimides will continue in the near future. The high solubility of carbon dioxide in certain polymers will ensure that polymers with high carbon dioxide/nitrogen solubility selectivity will increase in interest. For example, the polyimide/polyethylene oxide polymers described in Section 2.2.6 have excellent gas separation properties and are further of future research. Also of interest are polymers with a high fractional free volume. While most of polymers offer very high permeabilities and modest selectivities, some recent advances which also have moderate solubility selectivities have lead to excellent gas transport properties. Likewise, carbon membranes can offer excellent gas transport properties; however their fragility, difculty of manufacture and high cost impose signicant limitations on their utility. Mixedmatrix membranes offer a realistic technique to combine the gas transport properties of carbon membranes with the practicability of polymeric membranes. Additionally, while gas transport properties are important, it is equally important to ensure that membranes are physically durable and resistant to both chemical attack and plasticisation, while still being exible enough for manufacture into various membrane types. For reason, it is expected that future research will concentrate on improving these properties through techniques such as crosslinking after manufacture into appropriate membrane morphology.
24
Appendix A What follows is a listing of polymers with their structures and their carbon dioxide/nitrogen gas separation properties. A.1. Polyacetylenes (Figs. A1A3)
Fig. A1. Chemical structures of some polyacetylenes used in the formation of gas separation membranes.
25
Carbon dioxide and nitrogen gas permeability data for poly(acetylene) dense lms.
Name Poly(trimethyl-prop-1-ynyl-silane) Poly(3,3-dimethyl-but-1-yne) Poly(1-(dimethyl-trimethylsilanylmethyl-silanyl)-propyne) Poly(1-[dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propyne) Poly(trimethyl-(2-prop-1-ynyl-phenyl)-silane) Poly(1-prop-1-ynyl-2-triuoromethyl-benzene) Poly(dec-2-yne) Poly(1-chloro-dec-1-yne) Poly(1-chloro-oct-1-yne) Poly(1-chloro-hex-1-yne) Poly(hexyl-dimethyl-prop-1-ynyl-silane) Poly(trimethyl-(1-pentyl-prop-2-ynyl)-silane) Poly(hexyl-dimethyl-(1-propyl-prop-2-ynyl)-silane) Poly(prop-1-ynyl-benzene) Poly(but-1-ynyl-benzene) Poly(oct-1-ynyl-benzene) Poly(chloroethynyl-benzene) Poly(1-ethynyl-2-methyl-benzene) Poly(dimethyl-phenyl-(1-propyl-prop-2-ynyl)-silane) Temperature ( C) 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 P(CO2 ) (barrer) 19000 560 310 150 290 130 130 170 130 180 71 120 70 25 40 48 23 15 54 P(N2 ) (barrer) 1800 43 21 14 24 7.3 14 16 11 10 4.3 8.7 6.3 2.2 4.5 5.5 1.0 3.0 2.5 (CO2 /N2 ) 10.6 13.0 14.8 10.7 12.1 17.8 9.3 10.6 11.8 18.0 16.5 13.8 11.1 11.4 8.9 8.7 23.0 5.0 21.6 Reference [9] [9] [9] [9] [9] [9] [9] [9] [9] [9] [9] [9] [9] [9] [9] [9] [9] [9] [9]
A.2. Poly(arylene ether) (Fig. A4) Carbon dioxide and nitrogen gas permeability data for poly(arylene ether) dense lms.
Name 6FPT6FBPA 6FPTBPA 6FPPy6FBPA 6FPPyBPA Feed pressure (atm) 1.0 1.0 1.0 1.0 Temperature ( C) 35 35 35 35 P(CO2 ) (barrer) 25.29 18.53 29.46 21.44 P(N2 ) (barrer) 2.18 1.37 2.39 1.70 (CO2 /N2 ) 11.6 13.5 12.32 12.6 Reference [43] [43] [43] [43]
26
Fig. A4. Fluoro-containing novel poly(arylene ether).
A.3. Polyarylates (Figs. A5A7) Carbon dioxide and nitrogen gas permeability data for polyarylate dense lms.
Name BPA/IA BPA/tBIA HFBPA/IA HFBPA/tBIA PhTh/IA PhTh/tBIA FBP/IA FBP/tBIA TBBPA/IA TBBPA/tBIA TBHFBPA/IA TBHFBPA/tBIA TBPhTh/IA TBPhTh/tBIA TBFBP/IA TBFBP/tBIA DMBPA/IA DMBPA/tBIA TMBPA/IA TMBPA/tBIA DiisoBPA/IA DiisoBPA/tBIA DBDMBPA/IA PhAnth/IA PhAnth/tBIA FBP/IA FBP/tBIA Feed pressure (atm) 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 10/2 Temperature ( C) 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 P(CO2 ) (barrer) 5.4 24.2 19.1 56.9 6.74 23.8 12.4 36.8 4.93 21.5 25.6 85.1 8.34 30.6 20.4 69.5 1.24 8.0 12.0 44.6 5.16 16.1 5.45 9.0 25.9 12.4 36.8 P(N2 ) (barrer) 0.24 1.20 1.11 3.88 0.28 1.09 0.57 1.93 0.18 0.90 1.07 4.47 0.29 1.28 0.70 2.94 0.063 0.39 0.58 2.52 0.27 1.08 0.22 0.36 1.35 0.57 1.93 (CO2 /N2 ) 22.5 20.2 17.2 14.7 24.1 21.8 12.4 19.1 27.4 23.9 23.9 19.0 28.8 23.9 29.1 23.6 19.7 20.5 20.7 17.7 19.1 14.9 24.8 25 19.2 21.8 19.1 Reference [45] [45] [45] [45] [45] [45] [45] [45] [46] [46] [46] [46] [46] [46] [46] [46] [44] [44] [44] [44] [44] [44] [44] [47] [47] [47] [47]
27
Fig. A5. Structures of symmetric polyarylates used by Pixton and Paul [4446].
Fig. A6. Structures of asymmetric polyarylates used by Pixton and Paul [44].
28
Fig. A7. Structures of anthrone-based polyarylates studied by Pixton and Paul [47].
A.4. Polycarbonates (Figs. A8A10) Carbon dioxide and nitrogen gas permeability data for dense lms incorporating polycarbonates.
Name PC PC PC TMPC TMPC TCPC TBPC HFPC TMHFPC NBPC PCZ PCAP FBPC Feed pressure (atm) 10/5 1 10 1 10 1 1 10 10 10/2 10/2 2 2 Temperature ( C) 35 35 35 35 35 35 35 35 35 35 35 35 35 P(CO2 ) (barrer) 6.5 6.0 6.8 17.58 18.6 6.66 4.23 24 111 9.1 2.2 9.48 15.1 P(N2 ) (barrer) 0.33 0.289 0.32 1.09 1.0 0.36 0.182 1.6 7.4 0.47 0.105 0.361 0.592 (CO2 /N2 ) 19.7 21 21 16.1 18.6 18.5 23.2 15.0 15.0 19.4 21.0 26.3 25.5 Reference [50] [52] [51] [52] [51] [52] [52] [51] [51] [49] [49] [48] [48]
29
Fig. A8. Structures of some polycarbonates.
A.5. Poly(ethylene oxide) Carbon dioxide and nitrogen gas permeability data for poly(ethylene oxide) dense lms.
Name PEO PEO PEO PEO PEO PEO PEO EO/EM/AGE (80/20/2) EO/EM/AGE (77/23/2.3) EO/EM/AGE (96/4/2.5) Feed pressure (atm) 7.8 4.4 7.8 14.6 4.4 7.8 14.6 Not reported Not reported Not reported Temperature ( C) 25 35 35 35 45 45 45 35 35 35 P(CO2 ) (barrer) 8.1 13 15 17 40 46 52 773 680 580 P(N2 ) (barrer) 0.07 0.24 0.24 0.22 0.99 1.0 1.0 16.8 15.5 12.1 (CO2 /N2 ) 140 55 63 79 40 48 52 46 44 48 Reference [55] [55] [55] [55] [55] [55] [55] [56] [56] [56]
30
Fig. A9. Structures of some aromatic halogenated polycarbonates.
Fig. A10. Structures of some polycarbonates.
A.6. Polyimides (Figs. A11A15) Carbon dioxide and nitrogen gas permeability data for dense lms incorporating polyimides.
Name PMDABAPHF PMDA3BAPHF PMDA4,4 -ODA PMDA4,4 -ODA PMDA3,3 -ODA PMDA4,4 -ODA PMDA3,3 -ODA PMDAMDA Feed pressure (atm) 6.8 6.8 6.8 10 6.8 10/2 10/2 10 Temperature ( C) 35 35 35 35 35 35 35 35 P(CO2 ) (barrer) 11.8 6.12 1.14 2.71 0.50 1.18 3.55 4.03 P(N2 ) (barrer) 0.66 0.29 0.049 0.10 0.018 0.0454 0.145 0.20 (CO2 /N2 ) 17.8 21.1 23.3 27.1 27.8 26.0 24.5 20.2 Reference [74] [74] [74] [186] [74] [70] [70] [186]
31
Name PMDAIPDA PMDABAPHF PMDABATPHF BPDABAPHF BPDABATPHF BPDABAHF BPDABAFL BPDAmTrMPD BTDA4,4 -ODA BTDABAPHF BTDABATPHF BTDABAHF BTDAmTrMPD BTDABAFL PI oMeCatdurene mMeCatdurene DMeCatdurene mtBuCatdurene oMeptBuCatdurene TMeCatdurene mMetCatMDA mtBuCatMDA TMeCatMDA TMeCatTMB DBuCatTMB mtBuCatDMOB TMeCat6FiPDA 6F TMMPD IMDDM ODA Matrimid 5218
Feed pressure (atm) 10 10/2 10/2 10/2 10/2 10/2 1 10/2 10/2 10/2 10/2 10/2 10/2 1 10 1 1 1 1 1 1 1 1 1 1 1 1 1 3 3 3 3 10
Temperature ( C) 35 35 35 35 35 35 25 35 35 35 35 35 35 25 35 30 30 30 30 30 30 30 30 30 30 30 30 30 Not reported Not reported Not reported Not reported 35
P(CO2 ) (barrer) 29.7 17.6 24.6 4.95 9.15 27.7 23 137 0.625 4.37 6.94 10.1 30.9 15 2.00 27 20 63 71 67 200 22 63 110 39 95 6.7 54 114 600 196 25 6.5
P(N2 ) (barrer) 1.50 0.943 1.50 0.245 0.563 1.39 0.61 8.42 0.0236 0.195 0.370 0.45 1.55 0.39 0.063 0.83 0.59 2.05 2.55 2.5 8.1 0.65 2.2 3.8 1.2 4.9 0.21 1.9 5.8 35.1 10.8 0.97 0.25
(CO2 /N2 ) 19.8 18.7 16.4 20.2 16.3 19.9 37.7 16.3 26.5 22.4 18.8 22.4 19.9 38.5 31.7 33 34 31 28 27 25 34 29 30 33 19 32 28 19.6 17.1 18.1 25.8 25.6
Reference [186] [70] [70] [70] [70] [70] [187] [71] [70] [70] [70] [70] [71] [187] [60] [66] [66] [66] [66] [66] [66] [66] [66] [66] [66] [66] [66] [66] [107] [107] [107] [107] [57]
Fig. A11. Common polyimide moieties.
32
Fig. A12. Some diamine repeating units.
33
Fig. A13. Some diamine repeating units.
Fig. A14. Catechol-based polyimides synthesised by Kricheldorf and co-workers [66].
34
Fig. A15. Structures of some bulky novel polyimides.
A.7. 6FDA-based polyimides (Fig. A16) Carbon dioxide and nitrogen gas permeability data for dense lms incorporating the polyimide 6FDA.
Name 6FDApPDA 6FDApDiMPDA 6FDAdurene 6FDAdurene 6FDAmPDA 6FDAmPDA 6FDAmMPDA 6FDAmMPDA 6FDAmTrMPDA 6FDADATr 6FDADBTF 6FDAPHDoeP 6FDAPPDoeP 6FDAPMDoeP 6FDAPEPE 6FDAPBEPE 6FDAPTEPE 6FDAPMeaP 6FDA3,4 ODA 6FDAAPAP 6FDApp ODA 6FDABAPHF 6FDABATPHF 6FDABAHF 6FDA1,5-NDA Feed pressure (atm) 10 10 10 10 10 6.8 10 6.8 10 6.8 6.8 6.8 6.8 6.8 6.8 6.8 6.8 6.8 10 10 10 10 10 10 10 Temperature ( C) 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 P(CO2 ) (barrer) 15.3 42.7 440 456 9.20 8.23 40.1 42.52 431 28.63 21.64 8.59 15.05 4.78 6.88 2.50 1.94 2.41 6.11 10.7 16.7 19.1 22.8 51.2 23 P(N2 ) (barrer) 0.80 2.67 35.60 35.50 0.447 0.36 2.24 2.12 31.6 1.31 1.17 4.50 1.12 0.181 0.255 0.099 0.068 0.086 0.259 0.473 0.733 0.981 1.30 3.11 1.1 (CO2 /N2 ) 19.12 16.0 12.4 12.85 20.6 22.7 17.9 20.1 13.6 21.9 18.5 1.91 13.4 26.4 27.0 25.3 22.6 28.0 23.6 22.6 22.8 19.5 17.5 16.5 21 Reference [71] [71] [71] [65] [72] [72] [72] [72] [72] [72] [72] [69] [69] [69] [69] [69] [69] [69] [70] [70] [70] [70] [70] [70] [62]
35
Name 6FDAdurene 24 h amidation 6FDAdurene/mPDA (50/50) 6FDAdurene/mPDA (50/50) 4 h amidation 6FDAdurene/mPDA (50/50) 6 h amidation 6FDAdurene/mPDA (50/50) 12 h amidation 6FDAdurene/mPDA (50/50) 24 h amidation 6FDAdurene/mPDA (50/50) 48 h amidation 6FDAFDA/HFBAPP (1/1) 6FDAODA 6FDA4,4-ODA 6FDAMDA 6FDA4BDAF 6FDA3,3 -ODA 6FDA3BDAF 6FDAIPDA 6FDAIPDA 6FDAIPDA 6FDADAF 6FDADAF 6FDADAF PI-1 PI-3 PI-4 PI-5 6FDABAFL
Feed pressure (atm) 10 10 10 10 10 10 10 1.1 kg/cm2 10 6.8 10 6.8 6.8 6.8 10 10 10 10 10 10 1 1 1 1 1
Temperature ( C) Not Reported Not Reported Not Reported Not Reported Not Reported Not Reported Not Reported 30 35 35 35 35 35 35 35 45 55 35 45 55 30 30 30 30 25
P(CO2 ) (barrer) 11.6 84.6 54.9 49.1 46.0 36.0 24.5 465.0 23 22.0 19 19 2.1 6.3 24.3 25.6 27.4 19.5 20.2 21.3 32 360 62 190 98
P(N2 ) (barrer) 1.33 5.18 3.38 3.27 2.94 2.06 1.38 19.9 0.83 0.94 0.81 0.98 0.10 0.24 0.87 1.09 1.39 0.81 0.95 1.15 1.4 16.5 2.4 7.3 3.3
(CO2 /N2 ) 8.75 16.4 16.2 15.0 15.6 17.5 17.8 23.4 27.7 23.4 23.5 19.4 21 26.3 27.9 23.5 19.7 24.1 21.3 18.5 22.9 21.8 25.8 26.0 29.7
Reference [58] [58] [58] [58] [58] [58] [58] [68] [186] [74] [186] [74] [74] [74] [73] [73] [73] [73] [73] [73] [67] [67] [67] [67] [187]
Fig. A16. 6FDAterphenylene polyimides synthesised by Fritsch and co-workers [66].
36
Fig. A17. Structures of some poly(phenylene oxide) derivates.
A.8. Poly(phenylene oxide)s (Fig. A17) Carbon dioxide and nitrogen gas permeability data for poly(phenylene oxide) dense lms.
Name PPS PDMPO PDPPO PDMPO PDMPO (20.0% brominated) PDMPO (37.4% brominated) PDMPO (60.0% brominated) Feed pressure (atm) 1.5 1.5 1.5 689.1 kPa 689.1 kPa 689.1 kPa 689.1 kPa Temperature ( C) 35 35 35 22 22 22 22 P(CO2 ) (barrer) 1.60 65.5 39.9 90.0 93.6 97.1 159.9 P(N2 ) (barrer) 0.046 3.5 1.5 3.7 3.8 3.7 8.0 (CO2 /N2 ) 34.8 18.7 26.6 24.3 24.6 26.2 20.0 Reference [77] [77] [77] [76] [76] [76] [76]
A.9. Poly(pyrrolone) (Fig. A18) Carbon dioxide and nitrogen gas permeability data for polypyrrole dense lms.
Name 6FDATAB 6FDATADPO BBL Feed pressure (atm) 10/3 10/3 10/3 Temperature ( C) 35 35 35 P(CO2 ) (barrer) 54.0 27.6 0.12 P(N2 ) (barrer) 2.6 1.2 0.0026 (CO2 /N2 ) 20.8 23.0 46.3 Reference [79] [82] [81]
37
Fig. A18. Structures of some poly(pyrrolone)s.
A.10. Polysulfones (Figs. A19A22) Carbon dioxide and nitrogen gas permeability data for dense lms incorporating polysulfones.
Name PSF PSF TMPSF HFPSF TMHFPSF PSF-F PSF-O PSF-P TMPSF-F TMPSF-P BIPSF TMBIPSF 1,5-NPSF 2,6-NPSF 2,7-NPSF DMPSF HMBIPSF DMPSF-Z PSF-AP FBPSF PSF-M TMPSF-M PSF-BPFL 3,4 -PSF 1,3-ADM PSF 2,2-ADM PSF PSF (6% Br, 92% C CSiMe3 ) Feed pressure (atm) 10/5 10/>5 10/5 10/5 10/5 10/5 10/5 10/1 10/5 10/1 10/2 10/2 10/2 10/2 10/2 10/5 10/2 10/5 2 2 1 10/1 1 1 10/2 10/2 1 Temperature ( C) 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 25 35 35 35 35 P(CO2 ) (barrer) 5.6 4.9 21 12 72 4.5 4.3 6.8 5.5 13.2 5.6 31.8 1.6 1.5 1.8 2.1 25.5 1.4 8.12 13.8 2.8 7.0 10 1.5 7.2 9.5 36.5 P(N2 ) (barrer) 0.25 0.2 1.06 0.67 4.0 0.20 0.20 0.32 0.61 0.57 0.24 1.21 0.057 0.051 0.074 0.091 1.2 0.057 0.278 0.484 0.11 0.28 0.25 0.066 0.33 0.46 2.1 (CO2 /N2 ) 22.4 24.5 19.8 17.9 18 22.5 21.5 21.3 9.0 23.2 23.3 26.3 28.1 29.4 24.3 23.1 23.3 24.6 29.2 28.5 25.5 25.0 40 22.7 21.8 20.6 17.4 Reference [93] [50] [93] [94] [92] [94] [94] [90] [92] [90] [89] [89] [91] [91] [91] [93] [89] [93] [48] [48] [90] [90] [187] [90] [88] [88] [87]
38
Name PSF (3% Br, 47% C CSiMe3 ) PSF (21% Br, 77% C CCMe3 ) PSF (5% Br, 45% C CCMe3 ) PSF PSF-s-HBTMS PSF-o-HBTMS PSF-CH2 -TMS EM3 EM2 EM1 SM3 (degree of substitution = 2.0) SM3 (degree of substitution = 1.0) SM1 PPSF RM3 RM2 RM1 HFPSF HFPSF-o-HBTMS HFPSF-s-TMS HFPSF-o-TMS HFPSF-TMS TM6FPSF TM6FPSF-s-TMS TMPSF-TMS TMPSF-s-TMS TMPSF-HBTMS
Feed pressure (atm) 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
Temperature ( C) 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35
P(CO2 ) (barrer) 18.5 28.2 16.4 5.6 21 70 18 29 6.2 4.8 18 10 5.1 3.2 27 6.7 6.9 12.0 105 41 84 110 72 96 32 66.3 72
P(N2 ) (barrer) 1.24 1.7 0.9 0.25 0.96 3.29 0.95 1.3 0.24 0.16 0.77 0.38 0.17 0.10 1.9 0.60 0.61 0.67 5.63 2.0 4.7 6.3 4.0 5.2 1.51 3.07 3.36
(CO2 /N2 ) 14.9 16.6 18.2 22.4 22.2 21.3 18.9 22 26 30 23 26 30 32 14 11 11 17.9 18.6 20 18 18 18 19 21.3 21.6 21.4
Reference [87] [87] [87] [84] [84] [84] [84] [86] [86] [86] [86] [86] [86] [86] [86] [86] [86] [84] [84] [83] [83] [83] [83] [83] [85] [85] [85]
Fig. A19. Structures of PSF and some related methylated polymers.
39
Fig. A20. Some polysulfone structures.
Fig. A21. Some polysulfone structures incorporating bisphenol Z.
40
Fig. A22. Polysulfone structures incorporating aromatic substituted bisphenols.
A.11. Others (Figs. A23A27) Carbon dioxide and nitrogen gas permeability data for other polymeric dense lms.
Name HQDPAPDA HQDPAPDA HQDPADBA HQDPADBA HQDPAMDBA HQDPAMDBA HQDPAEDBA HQDPAEDBA 12H 6H6F 6F6H 12F PBK PBK-S PBSF PPES PPESK Feed pressure (atm) 7 7 7 7 7 7 7 7 5 5 5 5 10/2 10/2 10/2 Not reported Not reported Temperature ( C) 30 100 30 100 30 100 30 100 35 35 35 35 35 35 35 25 25 P(CO2 ) (barrer) 0.598 1.70 0.683 2.10 1.18 2.37 2.26 4.18 4.6 8.6 8.9 12.9 3.3 3.27 10.8 0.92 0.75 P(N2 ) (barrer) 0.016 0.111 0.015 0.125 0.034 0.160 0.077 0.292 0.21 0.44 0.42 0.76 0.13 0.11 0.47 0.027 0.042 (CO2 /N2 ) 37.4 15.3 45.5 16.8 34.7 14.8 29.4 14.3 21.9 19.5 21.2 17.0 25.4 29.7 23.0 34 18 Reference [53] [53] [53] [53] [53] [53] [53] [53] [189] [189] [189] [189] [188] [188] [188] [190] [190]
Fig. A23. PEI structure.
41
Fig. A24. PEI studied by Li and co-workers.
Fig. A25. Some poly(ether ketone) structures.
42
Fig. A26. Poly(arylether bissulfone)s and poly(arylether bisketone) studied by Paul and co-workers [188].
Fig. A27. Structure of poly(phthalazinone ether ketone) (PPEK) and poly(phthalazinone ether sulfone) (PPES).
A.12. Copolymers and polymer blends Carbon dioxide and nitrogen gas permeability data for copolymers and polymer blend dense lms.
Name 6FDATAB 6FDA/PMDATAB (50:50) 6FDA/PMDATAB (25:75) 6FDA/PMDATAB (10/90) 6FDATAB/DAM (75/25) 6FDATAB/DAM (50/50) 6FDADAM 6FDA/PMDA(1:6)TMMDA (CH2 Cl2 cast) 6FDA/PMDA(1:6)TMMDA (NMP cast) 6FDA/PMDA(1:6)TMMDA (DMF cast) MDIBPA/PEG(75) Feed pressure (atm) 10/3 10/3 10/3 10/3 3 3 3 10 10 10 2 Temperature ( C) 35 35 35 35 35 35 35 35 35 35 35 P(CO2 ) (barrer) 54.0 15.8 3.13 1.11 73.7 155 370 187 144 88.6 31 P(N2 ) (barrer) 2.8 0.70 0.098 0.036 3.1 6.6 29.5 11.7 8.76 5.16 0.70 (CO2 /N2 ) 19.3 22.6 31.9 30.8 23.8 23.5 12.5 16.0 16.4 17.2 44 Reference [79] [79] [79] [79] [115] [115] [115] [97] [97] [97] [112]
43
Name MDIBPA/PEG(80) MDIBPA/PEG(85) L/TDI(20)BPA/PEG(90) L/TDI(40)BPA/PEG(85) IPAODA/PEO3(80) BPDAODA/DABA/PEO1(75) BPDAmDDS/PEO1(80) BPDAODA/DABA/PEO2(70) BPDAODA/DABA/PEO2(80) BPDAODA/PEO3(75) BPDAmDDS/PEO3(75) BPDAmPD/PEO4(80) BPDAODA/PEO4(80) PMDAODA/DABA/PEO1(80) PMDAODA/PEO2(75) PMDAmPD/PEO3(80) PMDAAPPS/PEO3(80) PMDAAPPS/PEO4(70) PMDAmPD/PEO4(80) PMDAODA/PEO4(80) PMDApDDS/PEO4(80) PMDA/BTDABAFL (50:50) PMDA/BTDABAFL (90:10) BPDABAFL/HMDA (50:50) PPES PPES/PPEK (3:1) PPES/PPEK (1:1) PPES/PPEK (1:3) PPES/PPEK (1:4) PPEK HQDPADPA/MDPA HQDPADPA/MDPA HQDPADPA/EDPA HQDPADPA/EDPA PI PI/10PS PI/15PS PI/20PS PI/25PS PI/10PSVP PI/15PSVP PI/20PSVP PI/25PSVP NTDABDSA(30)/CARDO/ODA NTDABDSA(30)/CARDO NTDABDSA(30)/BAPHF NTDABDSA(30)/ODA 6FDAFDA/HFBAPP (1/1) 6FDAdurene/pPDA (80/20) 6FDAdurene/pPDA (50/50) 6FDAdurene/pPDA (20/80) 6FDAdurene/3,3 -DDS (75/25) 6FDAdurene/3,3 -DDS (50/50) 6FDAdurene/3,3 -DDS (25/75) 6FDA3,3 -DDS 6FDA6FpDA-DABA-12.5 6FDA6FpDADABA-12.5 annealed 6FDA6FpDADABA-12.5 (22.5% TMOS) 6FDA6FpDADABA-12.5 (22.5% TMOS) annealed 6FDA6FpDADABA-12.5 (15.0% MTMOS) 6FDA6FpDADABA-12.5 (15.0% MTMOS) annealed 6FDA6FpDADABA-12.5 (15.0% PTMOS) 6FDA6FpDADABA-12.5 (15.0% PTMOS) annealed 6FDA6FpDADABA-12.5 (22.5% PTMOS)
Feed pressure (atm) 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 1 1 1 Not reported Not reported Not reported Not reported Not reported Not reported 7 7 7 7 10 10 10 10 10 10 10 10 10 3 3 3 3 1.1 kg/cm2 10 10 10 10 10 10 10 4 4 4 4 4 4 4 4 4
Temperature ( C) 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 25 25 25 25 25 25 25 25 25 30 100 30 100 35 35 35 35 35 35 35 35 35 30 30 30 30 30 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35
P(CO2 ) (barrer) 48 59 47 35 58 2.7 3.8 14 36 75 72 81 117 14 40 99 159 136 151 167 238 43 130 0.54 0.92 2.94 4.12 2.06 1.77 0.75 0.957 2.34 1.34 3.25 2.00 2.33 2.32 2.90 4.29 3.58 3.71 5.65 6.55 70 164 23 5.2 465.0 230 126 59.26 84.7 19.8 5.12 1.84 34.0 70.8 30.9 47.6 44.0 110 32.3 91.8 30.7
P(N2 ) (barrer) 1.0 1.20 0.92 0.73 1.1 0.048 0.066 0.25 0.64 1.4 1.4 1.5 2.3 0.27 0.74 2.0 3.1 2.6 2.9 3.2 4.9 1.3 3.8 0.014 0.027 0.074 0.089 0.026 0.052 0.042 0.023 0.147 0.036 0.207 0.063 0.085 0.090 0.91 0.91 0.13 0.14 0.15 1.55 1.7 4.5 0.64 0.1 19.9 16.88 7.74 2.81 5.91 1.09 0.26 0.08 2.01 4.50 1.70 3.16 2.53 7.07 1.80 5.59 1.88
(CO2 /N2 ) 47 49 51 48 53 56 58 57 56 52 53 54 51 52 54 50 51 53 52 52 49 33 34 39 34 40 46 39 34 18 41.2 15.9 37.6 15.7 31.7 27.4 25.8 3.19 4.71 28.4 26.5 38.4 4.31 41 36 36 52 23.4 13.62 16.28 21.09 14.3 18.2 19.7 22.7 16.9 15.7 18.2 15.1 17.4 15.6 17.9 16.4 16.3
Reference [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [112] [187] [187] [187] [190] [190] [190] [190] [190] [190] [53] [53] [53] [53] [60] [60] [60] [60] [60] [60] [60] [60] [60] [63] [63] [63] [63] [68] [65] [65] [65] [61] [61] [61] [61] [59] [59] [59] [59] [59] [59] [59] [59] [59]
44
Name 6FDA6FpDADABA-12.5 (22.5% PTMOS) annealed 6FDA6FpDADABA-25 6FDA6FpDADABA-25 annealed 6FDA6FpDADABA-25 (22.5% TMOS) 6FDA6FpDADABA-25 (22.5% TMOS) annealed 6FDA6FpDADABA-25 (15.0% MTMOS) 6FDA6FpDADABA-25 (15.0% MTMOS) annealed 6FDA6FpDADABA-25 (22.5% MTMOS) 6FDA6FpDADABA-25 (22.5% MTMOS) annealed 6FDA6FpDADABA-25 (15.0% PTMOS) 6FDA6FpDADABA-25 (15.0% PTMOS) annealed 6FDA6FpDADABA-25 (22.5% PTMOS) 6FDA6FpDADABA-25 (22.5% PTMOS) annealed Poly(5:5 BPA/BN) Poly(7:3 BPA/BN)
Feed pressure (atm) 4 4 4 4 4 4 4 4 4 4 4 4 4 5 5
Temperature ( C) 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35
P(CO2 ) (barrer) 90.9 20.3 77.3 15.7 79.8 16.6 81.1 16.6 60.1 18.4 104 19.1 104 5.71 4.62
P(N2 ) (barrer) 5.87 1.20 4.85 1.06 4.87 1.07 5.07 1.07 3.83 0.94 6.25 0.98 6.25 0.19 0.16
(CO2 /N2 ) 15.5 16.9 15.9 14.8 16.4 15.5 16.0 15.5 15.7 19.6 16.6 19.5 16.6 30.1 28.9
Reference [59] [59] [59] [59] [59] [59] [59] [59] [59] [59] [59] [59] [59] [114] [114]
A.13. Cross-linking polymers Carbon dioxide and nitrogen gas permeability data for cross-linked membranes dense lms.
Name Poly(ethylene oxide-co-epichlorohydrin) (1:1) 1.1% Poly(ethylene oxide-co-epichlorohydrin) (1:1) 2% Poly(ethylene oxide-co-epichlorohydrin) (1:1) 5% DM14/MM9 (100/0) DM14/MM9 (100/0) DM14/MM9 (90/10) DM14/MM9 (90/10) DM14/MM9 (70/30) DM14/MM9 (70/30) DM14/MM9 (50/50) DM14/MM9 (50/50) DM14/MM9 (30/70) DM14/MM9 (30/70) DB30/MM9 (100/0) DB30/MM9 (100/0) DB30/MM9 (90/10) DB30/MM9 (90/10) DB30/MM9 (70/30) DB30/MM9 (70/30) DB30/MM9 (50/50) DB30/MM9 (50/50) DB30/MM9 (30/70) DB30/MM9 (30/70) DM9/MM9 (90/10) DM9/MM9 (90/10) DM23/MM9 (90/10) DM23/MM9 (90/10) DB10/MM9 (90/10) DB10/MM9 (90/10) DB69/MM9 (90/10) (cooling) DB69/MM9 (90/10) (cooling) DB69/MM9 (90/10) (heating) DB69/MM9 (90/10) (heating) DM14/MM23 (30/70) (cooling) DM14/MM23 (30/70) (cooling) DM14/MM23 (30/70) (heating) Matrimid 5218 Feed pressure (atm) 3 105 Pa 3 105 Pa 3 105 Pa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 96.7 kPa 10 Temperature ( C) 25 25 25 25 50 25 50 25 50 25 50 25 50 25 50 25 50 25 50 25 50 25 50 25 50 25 50 25 50 25 50 25 50 25 50 25 35 P(CO2 ) (barrer) 15.0 14.9 16.1 45 107 62 133 96 195 144 260 210 350 93 200 105 210 141 270 179 330 250 410 18.3 51 145 290 6.7 27 240 510 98 400 240 420 250 6.5 P(N2 ) (barrer) 2.3 1.0 0.5 0.66 2.8 0.90 3.4 1.5 5.4 2.25 7.2 3.3 10.6 1.5 5.7 1.6 5.8 2.1 7.7 2.9 9.7 4.2 12.4 0.3 1.3 2.2 7.6 0.11 0.79 4.3 14.2 1.6 11.4 3.9 12 4.0 0.25 (CO2 /N2 ) 6.52 14.9 32.2 68 38 69 39 66 36 64 36 63 33 63 35 64 36 67 35 62 34 60 33 68 38 66 38 61 34 56 36 62 35 62 35 62 25.6 Reference [125] [125] [125] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [126] [57]
45
Name Matrimid 5218, 1 day cross-linking Matrimid 5218, 3 days cross-linking Matrimid 5218, 7 days cross-linking Matrimid 5218, 14 days cross-linking Matrimid 5218, 21 days cross-linking Matrimid 5218, 32 days cross-linking 6FDAdurene, 5 min cross-linked 6FDAdurene, 10 min cross-linked 6FDAdurene, 15 min cross-linked 6FDAdurene, 30 min cross-linked 6FDAdurene, 60 min cross-linked
Feed pressure (atm) 10 10 10 10 10 10 10 10 10 10 10
Temperature ( C) 35 35 35 35 35 35 35 35 35 35 35
P(CO2 ) (barrer) 7.4 6.0 5.1 4.7 3.4 1.9 136 91.8 70.0 30.3 2.14
P(N2 ) (barrer) 0.29 0.24 0.21 0.19 0.15 0.13 11.1 6.53 6.05 2.87 0.40
(CO2 /N2 ) 25.6 25.2 24.6 24.1 22.2 15.0 12.3 14.1 11.6 10.6 5.35
Reference [57] [57] [57] [57] [57] [57] [64] [64] [64] [64] [64]
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Journal of Membrane Science 279 (2006) 149

Fig. 1. Oxygennitrogen selectivity vs. oxygen permeability (from Ref. [23]).

773.19 Data from Refs. [32,33].

Fig. 5. Example of polymeric structures.

Fig. 6. Selectivity vs. permeability of polymeric membranes.

Permeabilities in barrer, pressure = 2 atm, temperature = 35 C. Data from Ref. [96].

Fig. 7. Examples of high free fractional volume polymers.

Fig. 9. Carbon dioxide permeability vs. selectivity for polyarylates.

Fig. 10. TBHFBPA/tBIA.

Fig. 11. TMHFPC.

Fig. 12. Carbon dioxide permeability vs. selectivity for polycarbonates.

Scheme 1. Synthesis of 6FDApPDA.

Fig. 16. Matrimid 5218.

Fig. 17. Carbon dioxide permeability vs. selectivity for polyimides.

Fig. 13. Common dianhydrides used in the synthesis of polyimides.

Fig. 18. Polypyrrolone structures.

Fig. 14. Catechol-based dianhydrides.

Fig. 15. PITMMPA.

Scheme 2. Synthesis of 6FDATAB.

Fig. 19. 6FDA/PMDATAB.

Fig. 20. Adamantane-based polysulfone membranes.

Fig. 21. Naphthalene-based polysulfone membranes.

Fig. 22. Novel polysulfones-based off PSF.

Scheme 3. Synthesis of PSF.

Scheme 4. Synthesis of alkynylated PSF.

Fig. 23. Novel polysulfones-based off HFPSF.

Fig. 24. PPSF and novel polysulfones-based off PPSF.

Fig. 25. Novel polysulfones-based off TMPSF.

Fig. 26. Carbon dioxide permeability vs. selectivity for polysulfones.

Fig. 27. NTDABDSA/ODA.

Fig. 28. PMDApDDS/PEO4(80).

Fig. 29. 6FDATAB/DAM.

Scheme 5. Reaction of N,N-dimethylaminoethyleneamine and 6FDAdurene.

Scheme 6. Synthesis of poly(imide siloxane) copolymers.

Data from Ref. [72].

Permeabilities measured at 25 C. Data from Ref. [125].

Fig. 30. Monomers used by Hirayama et al. [126].

Fig. 31. FBP/XTA-C110/tBIA.

13.1 13.5 17.0 17.8 2.33 2.59 4.23

13.0 13.3 16.5 17.2 2.21 2.40 3.44

10.3 10.6 11.5 12.6 2.51 2.90 4.48

Data from Ref. [144].

For a dilute suspension of spheres in a matrix: Peff = Pc

Fig. 34. Structure of a typical asymmetric membrane (from Ref. [155]).

Fig. A4. Fluoro-containing novel poly(arylene ether).

Fig. A8. Structures of some polycarbonates.

Fig. A9. Structures of some aromatic halogenated polycarbonates.

Fig. A10. Structures of some polycarbonates.

Temperature ( C) 35 35 35 35 35 35 25 35 35 35 35 35 35 25 35 30 30 30 30 30 30 30 30 30 30 30 30 30 Not reported Not reported Not reported Not reported 35

Fig. A11. Common polyimide moieties.

Fig. A12. Some diamine repeating units.

Fig. A13. Some diamine repeating units.

Fig. A14. Catechol-based polyimides synthesised by Kricheldorf and co-workers [66].

Fig. A15. Structures of some bulky novel polyimides.

Feed pressure (atm) 10 10 10 10 10 10 10 1.1 kg/cm2 10 6.8 10 6.8 6.8 6.8 10 10 10 10 10 10 1 1 1 1 1

Fig. A16. 6FDAterphenylene polyimides synthesised by Fritsch and co-workers [66].

Fig. A17. Structures of some poly(phenylene oxide) derivates.

Fig. A18. Structures of some poly(pyrrolone)s.

Feed pressure (atm) 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

Fig. A19. Structures of PSF and some related methylated polymers.

Fig. A20. Some polysulfone structures.

Fig. A21. Some polysulfone structures incorporating bisphenol Z.

Fig. A22. Polysulfone structures incorporating aromatic substituted bisphenols.