WO2005113121A1 - Membrane composite a couche mince - Google Patents

Membrane composite a couche mince Download PDF

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Publication number
WO2005113121A1
WO2005113121A1 PCT/GB2005/002028 GB2005002028W WO2005113121A1 WO 2005113121 A1 WO2005113121 A1 WO 2005113121A1 GB 2005002028 W GB2005002028 W GB 2005002028W WO 2005113121 A1 WO2005113121 A1 WO 2005113121A1
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WIPO (PCT)
Prior art keywords
membrane
species
accordance
mixture
ofthe
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PCT/GB2005/002028
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English (en)
Inventor
Neil B. Mckeown
Peter M. Budd
Detlev Fritsch
Original Assignee
The University Of Manchester
Gkss Forschungszentrum Geesthact Gmbh
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Application filed by The University Of Manchester, Gkss Forschungszentrum Geesthact Gmbh filed Critical The University Of Manchester
Publication of WO2005113121A1 publication Critical patent/WO2005113121A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2275—Heterogeneous membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
    • B01D61/362—Pervaporation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0694—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring, e.g. polyquinoxalines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00

Definitions

  • the present invention relates to a thin layer composite membrane inco ⁇ orating a thin layer comprised of a microporous material of high intrinsic microporosity for the selective permeation and/or separation of a particular component of a fluid or solid/fluid mixture, methods for fabricating such a membrane and applications for such a membrane.
  • 'microporous material' is intended to encompass a material which may also be described as a 'nanoporous material'.
  • Separation processes of industrial relevance include: (i) separation of H 2 from hydrocarbons, N 2 or CO in, for example, the refinery industry; (ii) separation of CO 2 , H 2 O and H 2 S from natural gas (dewpointing, upgrading); (iii) air separation either to obtain enriched O 2 or N 2 for various applications; (iv) separation of volatile organic compounds (VOC) or lower hydrocarbons from air and other gases; (v) pervaporative separation from trace organic compounds found in aqueous streams; (vi) separation of low molecular weight compounds and oligomers from fluids especially organic solvents (nanofiltration).
  • VOC volatile organic compounds
  • permeable membranes For industrial application, permeable membranes must be capable of providing an acceptable level of selectivity of one component in a mixture over other components in the mixture whilst operating at an acceptable permeation rate. Since the permeation rate of molecules through the membrane generally depends linearly on the thickness of the membrane, membranes are usually designed to be as thin as possible to generate the highest possible permeation rates for gas separation. Unfortunately, the drive towards higher permeation rates leads to membranes which are so thin as to lack the necessary mechanical strength to retain their structural integrity during use and function efficiently. Composite membranes have therefore been developed which inco ⁇ orate at least one relatively thin selective membrane layer, typically a thin film, and a thicker porous supporting layer.
  • Table 1 lists a selection of known polymers exhibiting unusually high oxygen permeability. Unfortunately, as shown in Table 1, these materials exhibit relatively low selectivities for oxygen in preference to nitrogen. The permeability / selectivity relationship for the polymers listed in Table 1 and some additionally highly permeable polyimides 6 are included in the 'upper bound' plot shown in Figure 1 (see reference 6 for a description of Figure 1).
  • the polymers listed in Table 1 are distinguished by a very high accessible free volume. 9 This high, accessible free volume may be described as porosity on a molecular level. It is anticipated that other materials, in particular polymers, of high intrinsic microporosity should exhibit similarly high oxygen permeabilities.
  • Rigid polymer networks having large surface areas have been disclosed in WO-A- 2002/002838 (The Victoria University of Manchester) which describes "organic-based" microporous materials comprised of a 3 -dimensional network of planar po ⁇ hyrinic macrocycles covalently interconnected by linkers which impose a particular relative orientation on the macrocycle rings they interconnect.
  • Each such linker may connect two or more of the macrocyclic rings together and in the overall network the substantial majority (but not necessarily all) ofthe macrocyclic rings is associated with at least three, and ideally four, linkers each of which in turn links that macrocycle to at least one adjacent macrocycle so as to build up the overall 3-dimensional network.
  • the non-coplanar orientation ofthe planes of adjacent macrocycles ensures a microporous structure.
  • the rigid linkers maintain the non- coplanarity of the planes of adjacent macrocycles that would otherwise allow the coalescence of macrocycles and thus collapse the desired void space within the material. While these materials represent an important advance in this area of technology and should find application in a number of different fields it is by no means evident from WO-A-2002/002838 whether the materials disclosed therein would be suitable for use in composite membranes.
  • the properties of the support will also markedly influence the performance of a composite membrane.
  • the coil diameter of the solved polymer chains should be greater than the pore dimensions of the support so as to not fill and plug the pores which would reduce the overall permeability of the membrane. 13
  • the permeability of the support should be significantly higher than the selective membrane material so that the permeability of the support does not reduce the overall permeability of the composite membrane.
  • a resistance model approach was defined 1 and improved, 15 ' 16 from which it can be concluded that if the expected permeability of the selective membrane layer is below 10 % of the permeability ofthe support, no reasonable resistance of the support has to be taken into account and hence the selectivity of the selective membrane layer is not appreciably influenced. It is therefore desirable that the support should possess high porosity, a small mean pore size, a permeability which is significantly higher than that of the selective membrane layer and, of course, the support should be stable to the conditions used to fabricate the composite membrane and the conditions ofthe separation process, e.g. solvents, temperatures, feed pressures etc.
  • US 4,230,463 describes coating an integrally asymmetric membrane with a thin layer of highly permeable silicone rubber and found a selectivity well above the intrinsic selectivity of silicone rubber.
  • US 5,391,219 discloses a variety of elastomers, e.g. poly(4- methylpentene-1) or butadiene-styrene copolymer, to coat an integrally asymmetric polyimide membrane and found the same effect of increased separation factor with respect to the elastomer.
  • US 4,840,819 and US 4,806,189 also disclose processes for producing composite membranes where the pores of the support are filled by a liquid so as to improve the homogeneity of the selective membrane layer when applied to the surface of the porous support.
  • US 5,320,754 describes the use of perfluoroethers to wet the surface of a porous support prior to coating with a selective membrane material. The presence of the perfluoroether in the pores of the support is believed to prevent the selective membrane material from penetrating appreciably in to the support and thereby ensures the formation of a thin homogenous selective membrane layer on the surface ofthe support.
  • An object of the present invention is therefore to provide composite membranes exhibiting improved performance over current composite membranes.
  • a thin layer composite membrane inco ⁇ orating a selective layer comprising a microporous material and a porous supporting layer, wherein said microporous material comprises organic macromolecules comprised of first generally planar species connected by rigid linkers having a point of contortion such that two adj cent first planar species connected by the linker are held in non-coplanar orientation.
  • the first aspect of the present invention is based on the realisation that composite membranes can be provided inco ⁇ orating microporous materials which exhibit high intrinsic microporosity by virtue of the presence of suitable generally planar species connected by rigid linkers having a point of contortion.
  • the selective layer may comprise a microporous material in which said first generally planar species are other than po ⁇ hyrinic macrocycles.
  • the inventive membranes may inco ⁇ orate a selective layer comprising polydioxane A (1) which possesses a repeating unit of formula:
  • a membrane according to the first aspect of the present invention may also be provided inco ⁇ orating a selective layer comprised of a microporous material comprising organic macromolecules comprised of first generally planar species connected by rigid linkers predominantly to a maximum of two other said first species, said rigid linkers having a point of contortion such that two adjacent first planar species connected by the linker are held in non-coplanar orientation.
  • a composite membrane in accordance with the first aspect of the invention may be produced inco ⁇ orating a selective layer comprising a microporous material ofthe kind disclosed in WO-A-2002/002838 and described in more detail later in the specification.
  • the first generally planar species are planar po ⁇ hyrinic macrocycles and the linkers connect pyrrole residues of adjacent macrocycles so that the linkers restrain the adjacent macrocycles such that their po ⁇ hyrinic planes are in a non-co-planar orientation, hi this way, the microporous material is comprised of a rigid 3-dimensional 'network' of planar po ⁇ hyrinic macrocycles which exhibits high intrinsic surface area and may be represented by the following formula (II):
  • L represents a linker fused to, and connecting, pyrrole residues of adjacent po ⁇ hyrinic macrocycles
  • M represents a metal ion or 2H + (for a metal free macrocycle)
  • R is carbon or nitrogen.
  • Composite membranes in accordance with the first aspect ofthe present invention may be fabricated to inco ⁇ orate a selective layer as defined in the first aspect ofthe invention, of any desirable thickness. It is preferred that the selective layer has a thickness which is less than or equal to 10 ⁇ m and more preferably, less than or equal to 1 ⁇ m. It is envisaged that certain applications may require even thinner selective layers, consequently, the selective layer may have a thickness of approximately 0.5 ⁇ m, or possibly in the range 0.1 ⁇ m - 0.4 ⁇ m. Yet more preferably the selective layer may have a thickness of less than approximately 0.1 ⁇ m, most preferably approximately 0.05 ⁇ m.
  • the selective layer has a permeability which is less than the permeability of the supporting layer, i.e. the permeability of the supporting layer should be higher than the selective layer so that the permeability of the supporting layer does not reduce the overall permeability ofthe composite membrane.
  • the selective layer has a permeability which is less than 50 % of the permeability of the supporting layer and most preferably the selective layer has a permeability which is less than 10 % of the permeability of the supporting layer.
  • the supporting layer exhibits an intrinsic nitrogen permeability in the range 100 - 200 m 3 /m 2 h bar, more preferably approximately 150 m 3 /m 2 h bar.
  • the support should possess high porosity and a small mean pore size
  • the supporting layer preferably has a mean pore size of less than 25 nm, more preferably a mean pore size in the range 10 - 20 nm, and yet more preferably a mean pore size of approximately 15 nm.
  • the pore size of the supporting layer is highly uniform such that a relatively homogenous supporting layer surface is provided upon which the selective layer is to be applied.
  • the supporting layer preferably comprises an inorganic material, e.g. a ceramic material, or an organic polymeric material.
  • the supporting layer may comprise an organic polymeric material selected from the group consisting of a polyimide, a polyamideimide, a polyethersulfone, a polyacrylate, a polyphenylenesulf ⁇ de and polyacrylonitrile.
  • a preferred embodiment of the invention provides a composite membrane in accordance with the first aspect of the present invention in which a 46 ⁇ m thick film of the microporous material exhibits an intrinsic oxygen permeability of approximately 380 Barrer at 30 °C at an oxygen feed pressure in the range 200 - 300 mbar.
  • a further preferred embodiment of the invention provides a composite membrane according to the first aspect of the invention in which a 46 ⁇ m thick film of the microporous material exhibits an intrinsic oxygen/nitrogen selectivity of approximately 4 at 30 °C at an oxygen feed pressure in the range 200 - 300 mbar.
  • Yet further preferred embodiments of the invention afford a membrane according to the first aspect ofthe invention in which the membrane has an oxygen permeability of up to 5 m 3 /m 2 h bar at 25 °C and/or an intrinsic oxygen/nitrogen selectivity of up to 5 at 25 °C.
  • composite membranes in accordance with the present invention may be formed into any desirable membrane configuration, such as flat sheets or hollow fibres.
  • the selective layer in the membrane according to the first aspect of the present invention may comprise a microporous material in which said first generally planar species are other than po ⁇ hyrinic macrocycles.
  • a membrane according to the first aspect of the present invention may also be provided inco ⁇ orating a selective layer comprised of a microporous material comprising organic macromolecules comprised of first generally planar species connected by rigid linkers predominantly to a maximum of two other said first species, said rigid linkers having a point of contortion such that two adjacent first planar species connected by the linker are held in non-coplanar orientation.
  • the macromolecules are such that at least 70 %, more preferably at least 80 %, and most preferably at least 90 % by mole of the first planar species are connected (by the rigid linkers) to a maximum of two other planar species.
  • Particularly preferred microporous materials comprise a plurality of contorted polymer chains in which adjacent chains are prevented from packing together efficiently by virtue of their rigid contorted structure which results in such materials possessing intrinsic microporosity.
  • microporous materials possess intrinsic microporosity extending in three dimensions but may be considered as 'non-network' polymer materials since they do not have a cross-linked covalently bonded 3-dimensional structure such as that possessed by the po ⁇ hyrin-based materials disclosed in WO-A-2002/002838.
  • the intrinsic surface area of the microporous material may be at least 300 m 2 g "1 or at least 500 m 2 g "1 .
  • the surface area may be in the range 600 to 900 m 2 g "1 or 700 to 1500 m 2 g "1 .
  • the pore diameter and number average mass of the microporous material are the pore diameter and number average mass of the microporous material, for example, as compared to polystyrene standards and measured by gel permeation chromatography.
  • the microporous material comprised in the selective layer of the inventive membrane preferably has an average pore diameter of less than 100 nm and, more preferably, a pore diameter in the range 0.3 to 20 nm.
  • the inventive membrane preferably inco ⁇ orates a microporous material having a number average mass (compared to polystyrene standards) in the range 1 x 10 3 to 1000 x 10 3 amu, more preferably in the range 15 x 10 3 to 500 x 10 3 amu.
  • the inventive membrane may inco ⁇ orate a selective layer comprising a microporous material which has a number average mass in the range 20 x 10 3 to 200 x 10 3 amu, or 10 x 10 3 to 100 x 10 3 amu.
  • microporous materials enables the pore structure of membranes constructed from such materials to be functionalised to a high degree of specificity for a particular species over similar species.
  • chiral inner surfaces can be produced which may be useful in separation processes involving chiral molecules, such as amino acids.
  • membranes in accordance with the first aspect of the invention may include an additional entity selected from a catalyst species, an organometallic species, an inorganic species, at least one type of metal ion; and at least one type of metal particle.
  • the additional entity may for example be a metal-containing organic catalyst such as a phthalocyanine or po ⁇ hyrin.
  • a preferred example of an inorganic species is a zeolite.
  • a second aspect of the present invention provides a method for producing a thin layer composite membrane in accordance with the first aspect of the present invention inco ⁇ orating a selective layer comprising a microporous material and a porous supporting layer, the method comprising the steps of: i) dissolving the microporous material in a solvent to form a solution of the microporous material; ii) contacting the supporting layer with said solution; and iii) evaporating the solvent to provide said selective layer comprising the microporous material on the supporting layer.
  • the intrinsic microporosity ofthe microporous materials inco ⁇ orated in to membranes in accordance with the present invention is distinct from the microporosity induced within conventional glassy polymers in that it is not eliminated by aging (i.e. physical relaxation), annealing at elevated temperatures (e.g. between 100 °C and 300 °C), or the slow removal of solvent during film or membrane fabrication. Accordingly, the performance of composite membranes in accordance with the invention should be more reliable, predictable and controllable than known membranes.
  • the high intrinsic microporosity of the microporous materials inco ⁇ orated into composite membranes in accordance with the invention also provides the opportunity to produce membranes exhibiting significantly improved performance (gas permeability, selectivity, etc) than conventional membranes.
  • the supporting layer is contacted with said solution of the microporous material by dip-coating.
  • This process may be carried out at any convenient temperature, although it is preferred that the dip-coating process is carried out at room temperature and final drying ofthe thin film above room temperature.
  • the solvent is of medium polarity.
  • the solvent is preferably an organic solvent, which is preferably tetrahydrofuran or a halogenated hydrocarbon.
  • the halogenated hydrocarbon is chloroform.
  • Modifying the selective layer coating solution by addition of alternative or additional solvents with different solvent strengths to a preferred solvent for a particular selective layer material (e.g. THF may be considered a preferred solvent for PIM-1 coating solutions) during or after drying is a known method for controlling the quality ofthe final selective layer.
  • Solvents may be characterised by their 'polarity'. 19 A more useful concept has been developed which introduced three-dimensional solubility parameters. The Hansen parameters characterising solubility can be used to derive fractional parameters, from which a triangular graph can be plotted to facilitate convenient selection of suitable alternative or additional solvents.
  • Adding nonsolvents to a casting solution for preparation of asymmetric membranes is a 91 well known technique to improve the quality of the final selective layer.
  • fractional solubility parameters were plotted in a triangular graph to facilitate selection of appropriate additives (i.e. nonsolvents or swelling agents) close in solubility properties to the solvents THF and CHC1 3 .
  • the additives chosen for investigation were the hydrocarbons cyclohexanone, ethyl acetate and dioxane, although many other suitable additives could be used, such as aromatic or aliphatic hydrocarbons, alcohols, ethers, ketones or esters.
  • the solvent in which the microporous material is dissolved in step i) of the second aspect of the invention may contain an organic additive. It is preferred that the additive possesses a boiling point below 120 °C.
  • the additive may be selected from the group consisting of an aromatic hydrocarbon, an aliphatic hydrocarbon, an alcohol, an ether, a ketone, an ester and halogenated derivatives thereof.
  • the additive may be selected from the group consisting of allyl acetate, butyl acetate, propyl acetate, ethyl acetate.
  • the additive may be selected from the group consisting of 1,4-dioxane and 1,3-dioxolane.
  • Further preferred additives may be selected from the group consisting of diethyl ether, methyl ethyl ether, dibutyl ether and methyl-t-butyl ether, the group consisting of acetone, diethyl ketone dipropyl ketone, methyl butyl ketone, di-isobutyl ketone, methyl ethyl ketone, ethyl butyl ketone and cyclohexanone, or the group consisting of methanol, ethanol, n-propanol, iso-propanol and t-butyl alcohol.
  • additives are 1,1-dimethoxy ethane or additives selected from the group consisting of 1,1,1-trichloroethane and 1,1,2-trichloroethane.
  • concentration of the additive in the solvent may be chosen to suit a particular solvent/additive system and will also depend upon the nature of the selective layer, supporting layer and the final composite membrane to be produced.
  • concentration ofthe additive in the solvent therefore may be less than 50 %, less than 20 %, or in the range 1 % to 15 %.
  • concentration of the additive in the solvent may be relatively low, e.g. approximately 5 %.
  • Cross-linking of the microporous material is likely to modify the properties of the selective layer and the final composite membrane.
  • the microporous material is at least partly cross-linked by treatment with a cross-linking agent before, during or after contacting the supporting layer with the solution of the microporous material.
  • the cross-linking agent may be palladium dichloride.
  • Such cross-linking may render the membrane insoluble in organic solvents, which may be desirable in certain applications. While many microporous materials suitable for inco ⁇ oration in to membranes in accordance with the present invention are soluble in common organic solvents, some are not. Such insoluble materials may be formed into membranes using a range of conventional techniques such as powder pressing. Alternatively, insoluble microporous materials may be mixed with a soluble microporous material so that the mixture can then be processed using any of the known techniques employed for fabricating membranes from soluble materials e.g. solvent casting or dip- coating.
  • any desirable concentration of the microporous material in the solution of the microporous material may be used to suit a particular application, however, it is preferred that the microporous material is a relatively minor component of the solution. Accordingly, it is preferred that the concentration of the microporous material in the solution ofthe microporous material is less than 5 %, more preferably in the range 0.1 % to 2 %, or 0.5 % to 1.0 %. Most preferably the concentration ofthe microporous material in the solution ofthe microporous material is approximately 0.75 %.
  • the supporting layer may be treated with a first treatment solution before the supporting layer is contacted with the solution of the microporous material. It is preferred that the first treatment solution is substantially miscible with the solution ofthe microporous material.
  • the first treatment solution is preferably water or a hydrocarbon based liquid.
  • the first treatment solution may be an alcohol, such as isopropanol.
  • the first treatment solution may be tetrahydrofuran.
  • Optimisation of properties of the final composite membrane may be obtained by employing a method for producing the membrane in accordance with the second aspect of the invention in which the first treatment solution comprises a gas permeable polymer, e.g polydimethylsiloxane.
  • the concentration of polydimethylsiloxane in the first treatment solution is less than 1 %, more preferably less than 0.5 %.
  • the first treatment solution may be a halogenated hydrocarbon based liquid, such as a perfluoroether.
  • Properties of the final thin layer composite membrane may be modified by the application of a layer of a gas permeable polymer, such as polydimethylsiloxane, to the supporting layer before the supporting layer is contacted with the solution of the microporous material.
  • a gas permeable polymer such as polydimethylsiloxane
  • the composite membrane once formed may be treated with a second treatment solution, which may comprise a gas permeable polymer, such as polydimethylsiloxane or a fluorinated hydrocarbon.
  • a gas permeable polymer such as polydimethylsiloxane or a fluorinated hydrocarbon.
  • concentration of the gas permeable polymer in the second treatment solution is preferably low, i.e. less than 1 %, more preferably less than 0.5 %.
  • the second treatment solution may comprise a hydrocarbon based solvent, e.g. isooctane or a perfluoroether.
  • Separation processes for which composite membranes in accordance with the present invention may be particularly suitable include: separation of H 2 from hydrocarbons, N 2 or CO; separation of CO 2 , H 2 O and or H 2 S from natural gas (dewpointing, upgrading); enrichment of O 2 or N 2 in air; separation of volatile organic compounds (VOC) or lower hydrocarbons from air and other gases; pervaporative separation from trace organic compounds found in aqueous streams; and separation of low molecular weight compounds and oligomers from fluids especially organic solvents (nanofiltration).
  • a method for modifying the composition of a feed mixture comprising first and second species comprising the steps of: i) applying the feed mixture to a feed side of a membrane in accordance with the first aspect ofthe present invention; and ii) collecting a retentate possessing a different composition to the composition ofthe feed mixture from the feed side of the membrane and or collecting a permeate possessing a different composition to the composition of the feed mixture from an opposite side of the membrane.
  • the third aspect of the present invention provides a method employing an inventive thin layer composite membrane which is eminently suitable for use in nanofiltration processes in which it is desired to separate low molecular weight compounds and oligomers from fluids, in particular, organic solvents.
  • the first species may be a low molecular weight compound and the second species may be an organic solvent.
  • step ii) would preferably comprise collecting a retentate possessing a higher concentration ofthe low molecular weight compound compared to the composition of the feed mixture from the feed side of the membrane.
  • the percentage of the first species in the retentate compared to the percentage of the first species in the feed mixture is as high as possible, i.e. above 50 %, more preferably above 75 % and yet more preferably above 95 %. It is most preferred that the percentage of the first species in the retentate compared to the percentage of the first species in the feed mixture is approximately 99 %.
  • a method for separating a first species from a mixture of said first species and a second species comprising the steps of: i) applying the mixture to a feed side of a membrane in accordance with the first aspect of the invention; ii) causing the first species to pass through the membrane; and iii) collecting the first species from an opposite side of the membrane and or the second species from the feed side ofthe membrane.
  • the term 'separating' in the method forming this aspect of the invention is intended to encompass both 'separation' and 'removal' of a first species from a mixture of said first species and a second species.
  • an fifth aspect ofthe present invention provides a method for enriching a first species in a first mixture of said first species and a second species, the method comprising the steps of: i) applying the first mixture to a feed side of a membrane in accordance with the first aspect of the invention; ii) causing the first mixture to pass through the membrane; and iii) collecting a second mixture of the first and second species, which is enriched in respect of the first species compared to the first mixture, from an opposite side of the membrane and/or collecting a third mixture ofthe first and second species, which is enriched in respect of the second species compared to the first mixture, from the feed side ofthe membrane.
  • the mixture which is applied to the feed side of the membrane in step i) of the third, fourth or fifth aspects of the present invention may be in the gas or vapour phase, or alternatively, in the liquid phase.
  • the method in accordance with the third aspect of the invention is eminently suitable for modifying the composition of a mixture comprising a first species and at least two further species.
  • the fourth aspect of the invention is eminently suitable for the separation (or removal) of a first species from a mixture of said first species and at least two further species.
  • the method forming the fifth aspect ofthe invention is eminently suitable for the enrichment of a first species in a mixture of said first species and at least two further species.
  • the first and second species is an organic compound.
  • the first species is an organic compound and the second species is water.
  • the organic compound may be an alcohol or a halogenated hydrocarbon compound.
  • the first and second species are organic compounds and the first species is an isomer of the second species.
  • at least one of said organic compounds may be an alcohol or a halogenated hydrocarbon compound.
  • at least one of the first and second species may be a metal-containing compound.
  • the first species may be oxygen and the second species may be nitrogen.
  • Membrane separation is based primarily on the relative rates of mass transfer of different species across a membrane.
  • a driving force typically a pressure or a concentration difference, is applied across the membrane so that selected species preferentially pass across the membrane.
  • the inventive membranes may be used for purification, separation or adso ⁇ tion of a particular species in the liquid or gas phase.
  • the inventive membranes may, for example, be used for the separation of proteins or other thermally unstable compounds, e.g. in the pharmaceutical and biotechnology industries.
  • the membranes may also be used in fermentors and bioreactors to transport gases into the reaction vessel and transfer cell culture medium out of the vessel.
  • the membranes may be used for the removal of microorganisms from air or water streams (nanofiltration), water purification, ethanol production in a continuous fermentation/membrane pervaporation system, and detection or removal of trace compounds or metal salts in air or water streams.
  • the inventive membranes may be used in gas/vapour separation processes in chemical, petrochemical, pharmaceutical and allied industries for removing organic vapours from gas streams, e.g. in off-gas treatment for recovery of volatile organic compounds to meet clean air regulations, or within process streams in production plants so that valuable compounds (e.g., vinylchloride monomer, propylene) may be recovered.
  • gas/vapour separation processes in which the inventive materials may be used are hydrocarbon vapour separation from H 2 in oil and gas refineries, for hydrocarbon dewpointing of natural gas (i.e. to decrease the hydrocarbon dewpoint to below the lowest possible export pipeline temperature so that liquid hydrocarbons do not separate in the pipeline), for control of methane number in fuel gas for gas engines and gas turbines, and for gasoline recovery.
  • the membranes ofthe invention to inco ⁇ orate a species that adsorb strongly to certain gases (e.g. cobalt po ⁇ hyrins or phthalocyanines for O 2 or silver(I) for ethane) to facilitate their transport across the membrane.
  • inventive membranes may also be used in the separation of liquid mixtures by pervaporation, such as in the removal of organic compounds (e.g., alcohols, phenols, chlorinated hydrocarbons, pyridines, ketones) from water such as aqueous effluents or process fluids.
  • organic compounds e.g., alcohols, phenols, chlorinated hydrocarbons, pyridines, ketones
  • a membrane in accordance with invention which is ethanol-selective would be useful for increasing the ethanol concentration in relatively dilute ethanol solutions (5 - 10 % ethanol) obtained by fermentation processes.
  • Further liquid phase examples include the separation of one organic component from another organic component, e.g. to separate isomers of organic compounds.
  • Mixtures of organic compounds which may be separated using an inventive membrane include: ethylacetate- ethanol, diethylether-ethanol, acetic acid-ethanol, benzene-ethanol, chloroform-ethanol, chloroform-methanol, acetone-ispropylether, allylalcohol-allylether, allylacohol- cyclohexane, butanol-butylacetate, butanol-1-butylether, ethanol-ethylbutylether, propylacetate-propanol, isopropylether-isopropanol, methanol-ethanol-isopropanol, and ethylacetate-ethanol-acetic acid, as suggested by Tusel and Bruschke.
  • inventive composite membranes are eminently suitable for gas separation.
  • Exampl es of such separation include separation of an organic gas from a 'permanent' gas (i.e. a small inorganic gas such as nitrogen or oxygen), and the separation of organic gases from each other.
  • a 'permanent' gas i.e. a small inorganic gas such as nitrogen or oxygen
  • the inventive membranes may be used for separation of organics from water (e.g. ethanol and/or phenol from water by pervaporation) and removal of metal and organic compounds, low molecular weight compounds and/or oligomers from liquids such as water or organic solvents (nanofiltration).
  • An additional application for the inventive membranes is in chemical reactors to enhance the yield of equilibrium-limited reactions by selective removal of a specific product in an analogous fashion to the use of hydrophilic membranes to enhance esterification yield by the removal of water.
  • microporous materials to be employed in membranes in accordance with the present invention comprise first generally planar species connected by rigid linkers having a point of contortion such that that two adjacent first planar species connected by the linker are held in non-coplanar orientation.
  • the point of contortion is a spiro group, a bridged ring moiety, or a sterically congested single covalent bond around which there is restricted rotation.
  • the point of contortion may be provided by a substituted or unsubstituted spiro-indane, bicyclo-octane, biphenyl or binaphthyl moiety.
  • Each of the first planar species preferably comprises at least one aromatic ring.
  • each of the first planar species comprises a substituted or unsubstituted moiety ofthe formula:
  • inventive material may comprise repeating units of formula:
  • inventive material may comprise repeating units of formula:
  • microporous materials for inco ⁇ oration in to membranes of the present invention can be prepared with the type of chemistry used for the preparation of high performance polymers from a large variety of suitable monomers without compromising the intrinsic microporosity.
  • the robust chemical nature of the five and six-membered rings which dominate the structure of the microporous materials are similar to those chosen to construct high performance engineering materials and therefore promise improved chemical and physical stability as compared to PTMSP.
  • the inventive membranes inco ⁇ orate a selective layer comprising a class of microporous polymers, exemplified by polydioxane A (1), which offer similar (perhaps greater) microporosity than PTMSP due to their rigid and contorted molecular structure.
  • microporosity of polydioxane A (which represents a preferred embodiment of the present invention) is demonstrated by its high surface area (approximately 680 - 850 m 2 g " ) determined using nitrogen adso ⁇ tion measurements (BET calculation).
  • the presence of the cyano and methyl groups is optional, they may be omitted or replaced with other simple substituents.
  • Each phenyl group may contain one or more substituents.
  • the nature and arrangement of substituents on the spiro-indane moiety may be chosen to provide any desirable configuration around the carbon atom common to both 5-membered rings.
  • Polydioxane A may be prepared in good yield from the aromatic nucleophilic substitution reaction between a bis(catechol) (2) and tetrafluoroterephthalonitrile (3) as shown below in reaction scheme A:
  • polydioxane A (1) is freely soluble in THF and DMF, partially soluble in chloroform and insoluble in acetone, methanol and water.
  • gel permeation chromatography it has a number average mass of 170 x 10 3 amu as compared to polystyrene standards.
  • in solution as a powder and as a solvent cast membrane it is highly fluorescent (yellow). Most importantly, it displays a surface area in the range 680 - 850 m 2 g "1 (measured from 10 different samples).
  • Simple molecular modelling shows that polydioxane A (1) is forced to adopt a contorted configuration due to the presence of the spiro-indane centres, each of which acts as a "point of contortion'.
  • the fused ring structure ensures that the randomly contorted structure of each polymer molecule is locked so that the molecules cannot pack efficiently resulting in microporosity.
  • polydioxane A (1) Within the class of microporous polymers exemplified by polydioxane A (1) are five preferred sub-classes of microporous materials, each of which is characterised by the monomer units from which the final materials are produced.
  • the first sub-class of materials includes polydioxane A (1). Materials falling in to this sub-class are produced from the reaction of a Nu 2 -R-Nu 2 monomer and an X 2 -R"-X monomer.
  • R and R ⁇ represent organic-based moieties linking the Nu or X groups. R and R ⁇ may or may not be the same moiety. Provided at least one of R and R ⁇ contains at least one point of contortion, the resulting polymer will possess intrinsic microporosity.
  • R and/or R' may contain one or more point of contortion.
  • Nu represents a nucleophile and X represents a good leaving group for nucleophilic substitution, particularly aromatic nucleophilic substitution in cases where X is bonded to an aromatic group.
  • the reaction of Nu 2 -R-Nu 2 with X 2 -R 1 -X 2 involves a nucleophilic substitution reaction in which each Nu group bonds to a carbon atom bearing an X group and displaces X as exemplified below in idealised reaction scheme B.
  • Scheme B illustrates a preferred embodiment of the microporous materials to be inco ⁇ orated in to membranes in accordance with the present invention in which the four nucleophilic groups (Nu) in each monomer compound are arranged in two pairs in which the members of each pair are bonded to adjacent carbon atoms. Moreover the four leaving groups (X) in each monomer compound are likewise arranged in two pairs in which the members of each pair are bonded to adjacent carbon atoms. Arranging the four Nu and X groups in this way results in a pair of covalent bonds being formed to give a six-membered ring of atoms between each pair of monomers containing two carbon atoms from each monomer.
  • Each Nu and X may or may not be the same type of functional group. Moreover, each B and X may be any particular functional group provided it satisfies the above requirements.
  • Nu is an OH, NH 2 or SH group and X is a halogen, OPh, OTs or trif ⁇ ate group.
  • one monomer comprises suitably arranged nucleophilic groups which can react with suitably arranged leaving groups on another monomer so as to form a desired polymer.
  • a point of contortion may be present in the R-group of the nucleophile-containing monomer and not in the R'-group of the leaving group-containing monomer or vice versa. Additionally, a point of contortion may be present in both types of monomers.
  • the point of contortion is present in the monomer bearing the nucleophilic groups and that the generally planar species carry the leaving groups.
  • Structures 2 and 9 may be used as the racemate or R or S enantiomers.
  • R' and R' can be 2H (i.e. an etheno bridge) or a fused benzo unit (i.e. a triptycene).
  • a preferred point of contortion is provided by the spiro-indane moiety (substituted or unsubstituted).
  • a further preferred point of contortion comprises moieties linked by a sterically congested single covalent bond linking adjacent hydrocarbon moieties. By virtue of the steric congestion there is significant restriction of relative movement of the linked moieties around the single covalent bond.
  • X 2 -R'-X 2 monomers which represent the generally planar species are:
  • the point of contortion may be present in the monomer containing the leaving groups and the generally planer species may be the nucleophile-containing monomer.
  • the generally planer species may be the nucleophile-containing monomer.
  • reaction scheme C it may be desirable to convert a first nucleophile-containing monomer to a monomer containing leaving groups prior to reaction of the (newly formed) monomer containing leaving groups with a second nucleophile-containing monomer.
  • reaction scheme C One way in which this can be achieved is shown in reaction scheme C.
  • Reaction scheme C i) oxidation; ii) acetic acid, 100°C.
  • the second sub-class of materials are produced by reacting a (H 2 N) -R-(NH 2 ) 2 monomer with a (keto) 2 -R'-(keto) 2 or (keto)(hydroxy)-R'-(hydroxy)(keto) monomer.
  • the point of contortion may be present in the (keto) -R'-(keto) 2 or (keto)(hydroxy)-R'- (hydroxy)(keto) monomer alone, in which case the (H 2 N) 2 -R-(NH 2 ) 2 monomer represents the planar species (exemplified by reaction scheme D).
  • the point of contortion may be present in the (H 2 N) 2 -R-(NH 2 ) 2 monomer alone, in which case the (keto) 2 -R'-(keto) 2 or (keto)(hydroxy)-R'-(hydroxy)(keto) monomer represents the planar species (exemplified by reaction scheme E).
  • a point of contortion may be present in both the (keto) 2 -R-(keto) 2 / (keto)(hydroxy)-R-(hydroxy)(keto) monomer and the (H N) 2 - R-(NH 2 ) 2 monomer.
  • Compounds falling in to the third sub-class of materials are produced by the reaction of a nucleophilic monomer comprising an (H 2 N) 2 -R-(NH 2 ) 2 compound with a bis-anhydride or bis-dicarboxylic acid monomer.
  • the point of contortion may form part ofthe (H 2 N) -R-(NH 2 ) 2 monomer, bis-anhydride or bis-dicarboxylic monomer, or both types of monomers.
  • Reaction scheme F exemplifies the situation where the point of contortion, in this case a spiro-indane moiety, is contained in an acidic bis-anhydride monomer and the planar species is represented by the basic compound 1,2,4,5- tetraaminobenzene (46):
  • 1,2,4,5-tetraaminobenzene (46) may be substituted in reaction scheme F with any ofthe (H 2 N) 2 -R-(NH 2 ) 2 monomers described above (48, 53-61).
  • Examples of carboxylic anhydride or acid monomers which represent the planar species are shown below:
  • the overriding principle concerning compounds falling in to the second and third subclasses of materials is that one of the monomers comprises a plurality of nucleophilic groups (e.g. NH 2 ) and the other monomer comprises a plurality of electropositive carbon atoms bonded to electronegative atoms, such as oxygen atoms forming part of keto-, hydroxyl-, anhydrido- or carboxylic acid groups.
  • nucleophilic groups e.g. NH 2
  • electronegative atoms such as oxygen atoms forming part of keto-, hydroxyl-, anhydrido- or carboxylic acid groups.
  • the fourth sub-class of materials comprises compounds containing orthocarbonate groups.
  • any one of the Nu -R-Nu 2 compounds (2, 4-15, 34-42) is first converted to the corresponding bis-orthocarbonate compound, as exemplified in reaction scheme G:
  • the halogenated bis-orthocarbonate (68) may then be reacted with one ofthe planar Nu 2 - R-Nu 2 compounds (34-42) or one of the Nu 2 -R-Nu 2 compounds containing a point of contortion (2, 4-15), provided that at least one of the halogenated bis-orthocarbonate or the Nu 2 -R-Nu 2 compounds contains a point of contortion.
  • the halogenated bis-orthocarbonate (68) produced in reaction scheme H contains a point of contortion (the spiro-indane moiety) it can be reacted with either a planar Nu 2 -R-Nu 2 compound (34-42) or a Nu 2 -R-Nu 2 compound containing a further point of contortion (2, 4-15), as shown below in reaction scheme I, to produce a microporous material possessing intrinsic microporosity.
  • the halogenated bis-orthocarbonate did not contain a point of contortion it would have to be reacted with a Nu 2 -R-Nu 2 compound which did contain a point of contortion, e.g. any of compounds 2, 4-15.
  • the fifth sub-class of materials are formed by the reaction of a Nu 2 -R-Nu 2 monomer (2, 4-15, 34-42) with a compound containing a metal ion (such as Ti, Sn, Al, B, Ni, Cr, Co, Cd), or phosphorus or silicon (generally designated M in formula 70 below) as exemplified by the reaction of compound 2 below:
  • a metal ion such as Ti, Sn, Al, B, Ni, Cr, Co, Cd
  • M in formula 70 phosphorus or silicon
  • the Nu 2 -R-Nu 2 monomer may or may not contain a point of contortion as long as the repeating unit contains at least one point of contortion.
  • polymers may be made which contain any number of types of nucleophilic monomer bonded to any number of types of monomer comprising suitable leaving groups.
  • any number of types of sites of contortion may be combined with any number of types of rigid linker to produce a microporous organic material possessing the desired characteristics to suit a particular application.
  • microporous materials can be modified using simple reactions of the functional group(s) that they contain, e.g. hydrolysis of nitrile substituents (exemplified by reaction scheme K) and quaternarisation of amine functionality (exemplified by reaction scheme L). Such reactions may also be used to cross-link the inventive materials to render them insoluble, which may be desirable for certain applications.
  • the first aspect of the present invention provides thin layer composite membranes inco ⁇ orating a selective layer of a microporous material which comprises organic macromolecules comprised of first generally planar species connected by rigid linkers having a point of contortion such that two adjacent first planar species connected by the linker are held in non-coplanar orientation.
  • the first generally planar species are planar po ⁇ hyrinic macrocycles and the linkers connect pyrrole residues of adjacent macrocycles so that the linkers restrain the adjacent macrocycles such that their po ⁇ hyrinic planes are in a non-co-planar orientation.
  • Such microporous materials may be represented by the following formula (II):
  • L represents a linker fused to, and connecting, pyrrole residues of adjacent po ⁇ hyrinic macrocycles
  • M represents a metal ion or 2H + (for a metal free macrocycle)
  • R is carbon or nitrogen.
  • a composite membrane which inco ⁇ orates a selective layer comprising a microporous material ofthe general formula:
  • M represents a metal ion or 2H + (for a metal free macrocycle) and Li is a linker group.
  • the po ⁇ hyrin-based microporous material has an intrinsic surface area of at least 300 m 2 g _1 , more preferably at least 400 m 2 g "1 , and most preferably of 700 -
  • the inventive membrane may inco ⁇ orate a selective layer in which said po ⁇ hyrin-based microporous material is a phthalocyanine network possessing a basic repeating phthalocyanine repeating unit of formula:
  • the linkers may be such that the po ⁇ hyrinic macrocycles they interconnect are orthogonal to each other.
  • orthogonality is not essential and it is possible, for example, for the po ⁇ hyrinic planes of macrocycles connected by a linker to lie at angles of 60 to 90 ° to each other. It is also possible for the adjacent macrocycles connected by a linker to lie in parallel planes. In preferred embodiments the po ⁇ hyrinic plane of a macrocycle connected by the linker does not intersect any portion of another macrocycle connected by that linker.
  • the linkers which connect adjacent po ⁇ hyrin macrocycles preferably comprise planar fused ring systems connected by an at least one "orientating moiety" which provides for orientation of these rings systems such that the po ⁇ hyrinic plane of one macrocycle is not co-planar with that another macrocycle to which it is connected by the linker.
  • the fused ring systems of the linker each preferably comprise at least three fused rings and the fused rings of the linker are preferably six-membered rings.
  • the terminal fused ring systems may be ofthe formula:
  • the "orientating moiety” may be a substituted or unsubstituted spiro-indane moiety of formula:
  • the sides “c” are those sides that are fused to planar fused ring systems of the linker.
  • the "orientating moiety” may be a bridged ring entity to the sides of which are fused the terminal planar ring systems ofthe linker.
  • the bridged ring system is a bicyclo[2,2,0]octane ring.
  • a particularly preferred embodiment utilises a linker ofthe formula:
  • linker may be ofthe formula:
  • Figure 1 is an 'upper bound' plot of permeability verses selectivity for a range of polymers of high permeability
  • Figure 2 is a graphical representation of the temperature dependence of gas permeation for a 91 ⁇ m thick film of Polydioxane A (1);
  • Figure 3 is a schematic representation of a pervaporation rig employed in Example 2.
  • Figure 4 is a N 2 adso ⁇ tion/deso ⁇ tion isotherm for a 60 ⁇ m thick film of Polydioxane A
  • Figure 5 is a graphical representation of the variation in phenol concentration in a permeate solution as a function of phenol concentration in a feed solution for a series of phenol/water mixtures subjected to a pervaporation process using a 60 ⁇ m thick film of Polydioxane A (1);
  • Figure 6 is a graphical representation of separation factor and flux data for a series of phenol/water mixtures subjected to a pervaporation process using a 60 ⁇ m thick film of Polydioxane A (1);
  • Figure 7 is a graphical representation of the variation in ethanol concentration in a permeate solution as a function of ethanol concentration in a feed solution for a series of ethanol/water mixtures subjected to a pervaporation process using a 60 ⁇ m thick film of Polydioxane A (1) and the zirconia supported membrane of Example 1; and
  • Figure 8 is a graphical representation of separation factor and flux data for a series of ethanol/water mixtures subjected to a pervaporation process using a 60 ⁇ m thick film of Polydioxane A (1) and the zirconia supported membrane of Example 1.
  • a series of experiments have been conducted to investigate firstly the intrinsic properties of microporous materials to be used in the selective layer of composite membranes in accordance with the present invention. Thin layer composite membranes according to the invention were then tested for their permeance and selectivity to a range of gases. Treatment ofthe supporting layer prior to application of the selective layer, modification of the solvent system used during application of the selective layer and treatment of the composite membrane following application of the selective layer were investigated. Finally, preliminary experiments were carried out to assess the suitability ofthe inventive membrane to nanofiltration processes.
  • Polydioxane A (1) also refe ⁇ ed to herein as PIM-1, was prepared as described below and formed in to films of thickness 46 ⁇ m and 91 ⁇ m in accordance with the method set out below. Gas permeation data were then measured for a range of gases, which are listed in Tables 2 and 3.
  • the gases decreased in permeability according to: CO 2 > H 2 > He > O 2 > Ar > CH 4 , Propene > Xe > Propane.
  • CO 2 , H 2 , He, O 2 , N 2 , CH 4 , and Xe an increase of permeability with decreasing feed pressure was observed.
  • propene and propane a decrease of permeability with decreasing feed pressure was found.
  • P(O 2 ) at 320 bar feed pressure was 367 Ba ⁇ er and increased to 383 Ba ⁇ er at 76 mbar feed pressure.
  • Propene decreased from 202 Barrer at 690 mbar feed pressure to 126 Barrer at 190mbar. This behaviour is well known for polymers with extremely high free volume (Stern 1994).
  • PIM-N2 In comparison to PIM 1, PIM-N2 exhibited a higher selectivity but a lower permeability. Even though PIM-N2 exhibited a permeability for each gas which was approximately half that of PIM-1, it should be noted that the permeabilities for PIM-N2 are still acceptably high. Thus, these results indicate that PIM-N2 would also be suitable for the separation of O 2 or N2 from air, of CO 2 from N2, CH 4 and/or Xe, of H2 from N 2 and/or CH 4 .
  • the permeability of permanent gases e.g. oxygen, nitrogen etc
  • the permeability of permanent gases depends linearly on the thickness of the film. For extremely thin films close to monomolecular layers this dependence is no longer valid.
  • a gas permeability can be calculated for polymer films of thicknesses not to close to the monomolecular level.
  • the common polymer silicone rubber (PDMS) was selected and gas permeances of films of varied thickness were calculated for comparison to values calculated for the 91 ⁇ m PIM-1 film and 28 ⁇ m PIM-N2 film. The results of these calculations are shown in Tables 6 and 7.
  • PIM-1 PIM N2:
  • a solution of PIM-1 (1) was prepared in accordance with the method set out for the preparation of a 60 ⁇ m film and was then deposited on a porous zirconia ceramic support reinforced with metal mesh and left to dry under a stream of nitrogen.
  • PAN polyacrylonitrile
  • N 2 -permeance of 150 m 3 /m 2 h bar ( ⁇ 50) was selected, which should exceed the expected gas permeance of the selective layer by at least 10 times.
  • the reasoning underlying this selection is as follows. Assuming a selective layer thickness of 0.25 ⁇ m, a maximum permeance of about 40 m 3 /m 2 h bar was calculated for composite membranes of PIM-1 with the most permeable gas, CO 2 , at 100 % CO 2 . However, in a real separation mixture CO 2 will be a minor component (i.e. below 50 %) and it is reasonable to calculate permeances of up to 15 m 3 /m 2 h bar.
  • a PIM-1 / THF coating solution was prepared with low PIM-1 concentrations in the range 2.00 - 0.60 %.
  • a thin layer of each solution was applied by dip-coating to a PAN support using a coating machine to provide composite membranes having an area of 34 cm 2 .
  • the 60 ⁇ m thick film of PIM-1 (1) was tested using a standard batch pervaporation rig (Figure 3).
  • the circular flat membrane was clamped into a sealed glass test cell above a porous support with an elastomeric O-ring and a silicone rubber compound (RS), forming a leak free seal, giving a pervaporation area of 33.17 cm 2 .
  • the cell was filled with the feed solution (mixture of phenol in water; 400 mL) and a mechanical sti ⁇ er placed in the cell. Stirring was necessary to reduce the effects of concentration polarization arising from the high selectivity of the membrane and the low concentration of phenol in the feed.
  • Three samples were tested using feed solutions containing phenol in water at concentrations of 1, 3 and 5 wt.% phenol.
  • the cell temperature was controlled and measured with a thermocouple and electronic temperature control system.
  • the cell temperature was controlled at temperatures in the range 50-80 °C.
  • a vacuum pump on the downstream side maintained a low pressure.
  • the pressure was measured between the cell and the cold trap.
  • the permeate was condensed and frozen within the cold trap, which was cooled with liquid nitrogen.
  • the concentration of phenol in the permeate was measured by UV spectroscopy using the phenol abso ⁇ tion band at 270 nm.
  • (Y 1 /Y 2 ) is the weight ratio of component 1 (i.e., the organic compound) to component 2 (i.e., water) in the permeate and (X ⁇ IX 2 ) is the weight ratio of component 1 to component 2 in the feed.
  • a 60 ⁇ m thick film of PIM-1 (1) and a zirconia supported composite membrane were prepared as described above and tested using a standard batch pervaporation rig ( Figure 3) with a stainless steel test cell.
  • the circular flat membrane was clamped into the steel test cell above a porous support with an elastomeric O-ring and a silicone rubber compound (RS), forming a leak free seal, giving a pervaporation area of 24.6 cm 2 .
  • the cell was filled with the feed solution (mixture of ethanol and water, 400 mL). The solution was stirred to reduce the effects of concentration polarization. Samples were tested using feed solutions containing ethanol in water at concentrations in the range 10- 70 wt.%.
  • the cell temperature was controlled at 30 °C.
  • a vacuum pump on the downstream side maintained a low pressure.
  • the permeate was condensed and frozen within the cold trap, which was cooled with liquid nitrogen.
  • the concentration of ethanol in the permeate was measured using a calibrated refrac
  • a composite membrane inco ⁇ orating a support made from polyacrylonitrile (PAN) and a selective membrane layer comprising PIM-1 was prepared in accordance with Example 2.
  • Table 10 Feed pressure dependence of permeability for propene and propane.
  • a first membrane (Entry 7.1) consisted solely of the PAN support treated with a 0.25 % solution of cross-linkable PDMS in hexane.
  • a second membrane (Entry 7.2) consisted of the PDMS-treated support from Entry 7.1 coated with a 0.5 % solution of PIM-1 in THF.
  • Third and fourth membranes were investigate for comparative pu ⁇ oses to determine what effect, if any, a thicker defect free PDMS layer would have on the performance of the PAN support and PAN / PIM-1 composite membrane.
  • the third membrane (Entry 7.3) therefore consisted of a PAN support with a dense defect-free PDMS layer of- l ⁇ m thickness
  • the fourth membrane (Entry 7.4) consisted of the PDMS coated PAN support from Entry 7.3 coated with a PIM-1 selective layer (0.75 % PIM-1 solution in THF).
  • the PDMS-treated support prior to application of the selective membrane layer, exhibited a permeance to oxygen of around 100 m 3 /m 2 h bar (Entry 7.1), which is around two-thirds of that of the untreated support (approximately 150 m 3 /m 2 h bar).
  • a support with a dense defect-free PDMS layer of — l ⁇ m thickness (Entry 7.3) was investigated.
  • the supporting layer with a - l ⁇ m PDMS layer prior to coating with a PIM-1 solution exhibited an oxygen permeance of 4.90 m 3 /m 2 h bar and a selectivity of 2.00.
  • the permeance of the composite membrane (1.03 m 3 /m 2 h bar) was similar to that ofthe composite membrane inco ⁇ orating a support treated with a 0.25 % PDMS solution (0.93 m 3 /m 2 h bar) but the selectivity ofthe composite membrane inco ⁇ orating the thick PDMS layer was lower (3.02) than that of the membrane inco ⁇ orating the support treated with the dilute PDMS solution (3.46).
  • the thin film of the PBVI-1 polymer showed an unusual, marked adhesive strength on the PDMS layer.
  • a thinner PDMS layer (such as that provided by pre-treatment with a 0.25 % PDMS solution) can provide highly selective membrane layers at acceptably high gas permeances and that thicker defect-free PDMS layers are not necessarily required.
  • the quality of the final selective layer may be controlled by modifying the selective layer coating solution by addition of alternative or additional solvents with different solvent strengths to a prefe ⁇ ed solvent for a particular selective layer material during or after drying.
  • Suitable alternative or additional solvents were selected by use of a triangular graph plotted from fractional parameters derived from the Hansen parameters characterising solubility.
  • the hydrocarbons cyclohexanone, ethyl acetate and dioxane were chosen in order to investigate their effect on the formation of composite membranes in accordance with the present invention.
  • a first membrane (Entry 8.1) consisted of an untreated PAN support coated with a 1.0 % solution of PIM-1 in cyclohexanone.
  • a second membrane (Entry 8.2) consisted of an untreated PAN support coated with a 0.65 % solution of PIM-1 in a solvent mixture consisting of 13 % cyclohexanone in THF.
  • a third membrane (Entry 8.3) consisted of a PAN support pretreated with a liquid perfluoroether (FC-75) coated with a 0.65 % solution of PIM-1 in a solvent mixture consisting of 13 % cyclohexanone in THF.
  • a fourth membrane consisted of an untreated PAN support coated with a 0.69 % solution of PIM-1 in a solvent mixture consisting of 4.3 % ethyl acetate in THF.
  • a fifth membrane consisted of a PAN support pretreated with a liquid perfluoroether (FC-75) coated with a 0.69 % solution of PIM-1 in a solvent mixture consisting of 4.3 % ethyl acetate in THF.
  • a sixth membrane consisted of a PAN support pretreated with a liquid perfluoroether (FC-75) coated with a 0.43 % solution of PIM-1 in a solvent mixture consisting of 9 % dioxane in THF.
  • the coating solution consisting of a 0.65 % PIM-1 solution in 13 % cyclohexanone / THF (Entry 8.2) provided a composite membrane which exhibited a low O 2 - ⁇ ermeance (0.09 m 3 /m 2 h bar) and low selectivity (2.4).
  • Pretreatment ofthe PAN support with FC-75 prior to coating increased the selectivity to 3.49 at a low O 2 -permeance (0.08 m 3 /m 2 h bar).
  • Using the low O 2 -permeance values measured for Entries 8.2 and 8.3 allowed the calculation of effective selective layer thickness of 10.0 ⁇ m and 14.0 ⁇ m respectively.
  • the oxygen permeance of the untreated composite membrane formed using the 4.3 % ethyl acetate / THF solution was seven times higher than that of the untreated membrane formed using the 13 % cyclohexanone / THF solution (Entry 8.2) and 9 times higher than that of the unsupported 46 ⁇ m PIM-1 film (Table 2).
  • Pretreatment of the PAN support with FC-75 prior to coating further increased the selectivity to 4.60 at an O 2 -permeance of 0.50 m 3 /m 2 h bar.
  • the O - ⁇ ermeance values were used to calculate effective selective layer thickness of 1.6 ⁇ m and 2.0 ⁇ m for the composite membranes inco ⁇ orating the non-pretreated and pretreated supports respectively.
  • Dioxane as an additive at low PIM-1 concentration (0.43 %) provided a composite membrane which exhibited a reasonably high O 2 -permeance of 1.4 m 3 /m 2 h bar but at a selectivity below the intrinsic selectivity (4.0) of the unsupported 46 ⁇ m PIM-1 film (Table 2) and the selectivities of the other four composite membranes produced using a method employing THF as the predominant solvent (Entries 8.2 - 8.5).
  • treating the composite membrane following its formation i.e. after the selective membrane layer has been formed on the supporting layer, may also modify membrane performance such that membrane properties could be controlled to suit a particular application.
  • a composite membrane in accordance with the present invention consisting of an untreated PAN support coated with a 0.69 % solution of PIM-1 in a solvent mixture consisting of 4.3 % ethyl acetate in THF was produced (co ⁇ esponding to the membrane denoted Entry 8.4 in Table 13).
  • the composite membrane was immersed for 20 minutes in n-hexane, dried for 30 minutes in ventilated air at room temperature and finally coated with a 0.35 % solution of PDMS in isooctane.
  • the O 2 -permeance of the composite membrane before immersion in n-hexane was 0.40 m 3 /m 2 h bar. Following immersion in n-hexane the O 2 -permeance increased initially to 22.24 m 3 /m 2 h bar and fell slightly to 21.21 m 3 /m 2 h bar one hour later. Following coating with a dilute, crosslinkable PDMS solution (0.35 % PDMS in isooctane) the O 2 - permeance fell to 2.6 m 3 /m 2 h bar.
  • the selectivity of the untreated composite membrane was 4.9 and fell to 2.8 following treatment although it is worth noting that the selectivity of the treated membrane is above the intrinsic selectivity ofthe PDMS thin film given in Table 7.
  • a composite membrane inco ⁇ orating a support made from PAN and a selective membrane layer comprising PIM-1 was prepared in accordance with Example 2 using a PIM-1 concentration of 0.60 % in THF (co ⁇ esponding to the membrane denoted Entry 5.4 in Table 8).
  • the membrane was coated with a 0.35 wt% solution of Teflon AF 2400 in FC-75.
  • the permeances for a range of gases were measured at room temperature and used to calculate selectivities relative to nitrogen. The results are presented in Table 15.
  • the marked increase of permeability is explained by a swelling of the unsupported thin film and a widening of the microporous polymer network.
  • This can be influenced by directed crosslinking of the polymer chains as described above in relation to the microporous materials suitable for inco ⁇ oration into the inventive membranes. It will be evident to the skilled person that partial crosslinking of the polymer chains will obstruct swelling and hence result in a less pronounced increase in permeance.
  • Preliminary nanofiltration testing was carried out using a composite membrane inco ⁇ orating a support made from PAN and a selective membrane layer comprising PDVI-1 prepared in accordance with Example 2 using a PIM-1 concentration of 0.60 % in THF (corresponding to the membrane denoted Entry 5.4 in Table 8).
  • the composite membrane permeates O 2 at 4.16 m 3 /m 2 h bar and an effective layer thickness of 0.3 ⁇ m was calculated for the separation layer.
  • PDVI-1 (1) prepared as set out above was dissolved in THF (2-5 wt-%) and cast on a glass plate. After evaporation of the solvent and drying dense, clear, yellow films were obtained. Gas permeation data were measured at 30°C with pure gases using a pressure increase time-lag apparatus operated at low feed pressure (typically at 200-300 mbar). Permeation (P) was calculated from the slope in the steady state region, apparent diffusion (O app ) coefficients from the time-lag and so ⁇ tion by division ofPfD app .
  • PIM-N2 (74) was prepared as set out above and a 28 ⁇ m film formed from CHC1 3 solution.

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Abstract

L'invention concerne une membrane composite en couche mince incorporant une couche sélective comprenant une matière microporeuse et une couche de support poreuse. La matière microporeuse comprend des macromolécules organiques comportant des premières espèces généralement planes reliées à des lieurs rigides présentant un point de contorsion, de sorte que les deux espèces planes adjacentes reliées par un lieur sont maintenues dans une orientation coplanaire.
PCT/GB2005/002028 2004-05-22 2005-05-23 Membrane composite a couche mince WO2005113121A1 (fr)

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US11394082B2 (en) 2016-09-28 2022-07-19 Sepion Technologies, Inc. Electrochemical cells with ionic sequestration provided by porous separators
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US11545724B2 (en) 2016-12-07 2023-01-03 The Regents Of The University Of California Microstructured ion-conducting composites and uses thereof
CN114870652B (zh) * 2022-05-10 2024-05-31 镇江猎盾特种材料有限公司 一种卟啉基共轭微孔聚合物共混超滤膜及制备与应用

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