A METHOD FOR PRODUCING A GAS SEPARATION ARTICLE AND USE THEREOF

Abstract

The present disclosure provides a method for producing a gas separation article, said gas separation article comprising: a gas separation membrane, optionally a support, and optionally an additional support, said method comprising the steps of: a) providing a matrix, said matrix having a viscosity from 1 centipoise to 40000 centipoise, said matrix comprising or consisting of one or more monomers, oligomers and/or polymers, and optionally a solvent, b) contacting the matrix of step a) with a support comprising at least one side, said at least one side facing said matrix, thereby forming (i) a matrix side contacting the support and (ii) a matrix side opposite the side contacting the support, c) optionally contacting the matrix side opposite the side contacting the support with an additional support, d) subjecting said matrix contacted with said support to one or more electric fields that is/are substantially parallel to a plane in which the support extends, or substantially perpendicular to a plane in which the support extends e) fixating the one or more monomers, oligomers and/or polymers of the matrix subjected to one or more electric fields in step d) thereby forming a solid gas separation membrane, and f) optionally removing the support and/or the additional support.

The present disclosure also gas separation article obtainable by the aforementioned method as well as use of said gas separation article for separation of gases in a gas mixture.

Claims

1. A method for producing a gas separation article, said gas separation article comprising: a gas separation membrane, and a support said method comprising the steps of: a) providing a matrix, said matrix having a viscosity from 1 centipoise to 40000 centipoise, and said matrix comprising or consisting of one or more monomers, oligomers and/or polymers, b) contacting the matrix of step a) with a support comprising at least one side, said at least one side facing said matrix, thereby forming (i) a matrix side contacting the support and (ii) a matrix side opposite the side contacting the support, c) subjecting said matrix contacted with said support to one or more electric fields that is/are substantially parallel to a plane in which the support extends, or substantially perpendicular to a plane in which the support extends d) fixating the one or more monomers, oligomers and/or polymers of the matrix subjected to one or more electric fields in step d) thereby forming a solid gas separation membrane.

2. The method according to claim 1, wherein the matrix does not comprise solid particles.

3. The method according to claim 1, wherein the fixating in step d) converts the one or more monomers and/or oligomers into one or more of the following polymers: polyurethane, polyether block amide, polyimide, polydimethylsiloxane, polyethylene glycol, ethylene acrylic elastomer, perfluoropolymers, polymerized ionic liquids, polysulfone, polyamide, polyvinylamine, polyallylamine, polyethyleneimine, cyanoacrylates, rosin acrylates, ester acrylates, urethanes acrylates, silicone acrylates, amine acrylates, epoxy acrylates, epoxide groups, polyethylene, poly(tetramethylene oxide), polyethylene oxide, polyphenylene oxide, polydioxolane

4. The method according to claim 1, wherein the matrix comprises or consists of one or more polymers, said one or more polymers being one or more of the following: polyurethane, polyether block amide, polyimide, polydimethylsiloxane, polyethylene glycol, ethylene acrylic elastomer, perfluoropolymers, polymerized ionic liquids, polysulfone, polyamide, polyvinylamine, polyallylamine, polyethyleneimine, cyanoacrylates, rosin acrylates, ester acrylates, urethanes acrylates, silicone acrylates, amine acrylates, epoxy acrylates, epoxide groups, polyethylene, poly(tetramethylene oxide), polyethylene oxide, polyphenylene oxide, polydioxolane.

5. A method according to claim 1, wherein the support is porous.

6. A method according to claim 1, wherein the support is non-porous.

7. A method according to claim 1, wherein the gas-separation article further comprises an additional support.

8. The method according to claim 1, wherein the support and/or the additional support independently comprise one or more of the following: polyethylene terephthalate (PET), polysiloxanes, polydimethylsiloxane (PMDS), poly(1-trimethylsilyl-1-propyne) (PTMSP), polyacrylonitrile (PAN), perfluoropolymers, perfluoroethers (PTFE), polyvinylidene fluoride (PVDF), polyether sulfones (PES), polysulfones (PSU), polyimides (PI), polyetherimides (PEI), polyamides, polyamideimides, polycarbonates (PC), polyesters, polyether ether ketone (PEEK), poly(ethylene oxide) (PEO), polyacrylates, polymethacrylates, cellulose acetate, polyethylene (PE), polypropylene (PP) polytetrafluoroethylene (PTFE), polymethylpentene (PMP) and copolymers thereof.

9. The method according to claim 1, wherein the one or more electric fields is/are alternating electric field(s).

10. The method according to claim 1, wherein step c) comprises orienting the one or more monomers, oligomers and/or polymers to be substantially parallel to the one or more electric fields.

11. (canceled)

12. The method according to claim 10, wherein the one or more electric fields is/are provided parallel to a plane in which the support extends and only to a first side of the support, said first side of the support being opposite the side of the support facing the matrix.

13. The method according to claim 1, wherein the one or more electric fields is/are provided by an interdigitated electrode.

14. The method according to claim 1, wherein the one or more electric fields is/are substantially perpendicular to a plane in which the support extends.

15. The method according to claim 1, wherein the fixating in step d) comprises curing.

16. The method according to claim 15, wherein the curing comprises one or more of the following: heat, radiation, electron beams, chemical additives, moisture.

17. The method according to claim 1, wherein the matrix comprises a solvent, and the fixating in step d) comprises evaporation of said solvent.

18. The method according to claim 1, wherein the fixating of step d) comprises solidifying of the matrix.

19. A gas separation article obtainable by the method according to claim 1.

20. Use of a gas separation article according to claim 19 for separation of gases in a gas mixture comprising one of more of the following: oxygen and nitrogen, carbon dioxide and methane, carbon dioxide and natural gas, carbon dioxide and biogas, carbon dioxide and nitrogen hydrogen sulfide and methane; hydrogen sulfide and natural gas, hydrogen sulfide and biogas, hydrogen and methane, helium and methane, helium and hydrogen, hydrogen and carbon dioxide, helium and carbon dioxide, nitrogen and methane, hydrogen and nitrogen, hydrogen and ammonia hydrogen and carbon monoxide. propene and nitrogen, ethylene and nitrogen, ethylene and argon, vapor and natural gas.

21. Use according to claim 20, wherein the gas mixture comprises one or more of the following: carbon dioxide and natural gas, carbon dioxide and nitrogen, oxygen and nitrogen, hydrogen and nitrogen, vapor and natural gas, hydrogen and carbon dioxide.

22. Use according to claim 20, wherein the gas mixture comprises carbon dioxide and natural gas.

Description

DESCRIPTION OF THE DRAWINGS

[0032] FIG. 1 shows a process for producing a gas separation article as described herein comprising use of an interdigitated electrode. The electric field generated by the electrode is parallel to the plane in which the support extends. The use of an additional support is also shown. The arrow shows the direction of the electric field. In FIG. 1, the numbers designate the following: 1 is matrix, 2 is support, 3 is roll, 4 is additional support, 5 is direction of the electric field, 6 is electrode, 7 is curing chamber, 8 is solidified matrix.

[0033] FIG. 2 shows a process for producing a gas separation article comprising use of a top electrode and a bottom electrode. The electric field generated by the electrodes is perpendicular to the plane in which the support extends. The use of an additional support is also shown. The arrow shows the direction of the electric field. In FIG. 2, the numbers designate the following: 1 is matrix, 2 is support, 3 is roll, 4 is additional support, 5 is direction of the electric field, 6 is top electrode, 7 is bottom electrode, 8 is curing chamber, 9 is solidified matrix.

[0034] FIG. 3A shows the CO.sub.2 permeability as a function of the amount of PEGDME in Pebax 2533.

[0035] FIG. 3B shows CO.sub.2/N.sub.2 selectivity as a function as a function of the amount of PEGDME in Pebax 2533.

[0036] The disclosure is further illustrated by the following non-limitative Examples.

EXAMPLES

Abbreviations

[0037] STP Standard Temperature and Pressure such as according to the International Union of Pure and Applied Chemistry (IUPAC) and the National Institute of Standards and Technology (NIST). [0038] atm atmosphere [0039] VS versus [0040] kHz kilo Herz [0041] V Volt

Example 1

Effect of Electric Field Exposure on the Gas Permeation Performance

[0042] The effect of electric field exposure on the gas permeation performance of a commercially available UV-curable acrylated polyurethane was tested (Norland optical adhesive 65 purchased from Tech Optics Limited). The samples, i.e. membranes, were made on a roll to roll set up (R2R) in the absence of an electric field (i.e. not aligned sample) or in the presence of an alternating electric field at 10 kHz and 600 V (i.e. aligned sample). Except for the electric field, both not aligned and aligned samples were made using the same conditions. The aligned samples were either aligned in-plane or through-plane, using the electrode geometries in FIG. 1 and FIG. 2 respectively. No particles were added to the acrylated polyurethane polymer. The membrane thickness was set to 45 μm for all the samples.

[0043] Single gas permeation tests for N.sub.2 and CO.sub.2 across the membranes were performed at 23° C., using a conventional constant volume/variable pressure method. Prior to the test the membranes were dried under vacuum at 45° C. overnight. The upper pressure was kept constant at 2.0 bar for all the gases.

[0044] The results presented in Table 1 below show a clear difference in gas transport properties between not aligned polymer membranes (NAL) compared with the membrane exposed to electric field, which was either through-plane aligned (TPA) or in-plane aligned (IPA). [0045] The CO.sub.2 permeability, P, was found to be highest for the through-plane aligned membrane, and lowest for the in-plane aligned membrane. The not aligned membrane had a permeability between that of the through-plane aligned membrane and the in-plane aligned membrane. Thus, P(CO.sub.2); TPA>NAL>IPA [0046] The selectivity, α, for CO.sub.2 was found to be highest for the in-plane aligned membrane and lowest for the not aligned membrane. The through-plane aligned membrane had a selectivity between that of the in-plane aligned membrane and the not aligned membrane. Thus, α(CO.sub.2/N.sub.2); IPA>TPA>NAL

[0047] Thus, the TPA membrane shows best performance in terms of permeability, whereas the IPA membrane has the best selectivity.

TABLE-US-00001 TABLE 1 Pure gas permeability results for polymeric membranes made from NOA 65. P(CO.sub.2) P(N.sub.2) Selectivity Membrane Barrer Barrer α(CO.sub.2/N.sub.2) NAL 1.01 0.04 26.6 TPA 1.59 0.03 50.6 IPA 0.79 0.014 55.5

[0048] It was observed that through plane alignment significantly increased both the CO.sub.2 permeability (P), and the CO.sub.2/N.sub.2 selectivity compared to the sample without alignment (i.e. NAL). In plane alignment also increased CO.sub.2/N.sub.2 selectivity but with a decreased CO.sub.2 and N.sub.2 permeability compared to the sample without alignment (i.e. NAL). Thus, the application of an electric field improved the permeability and/or selectivity.

Example 2

[0049] Enhanced Permeability and Maintained Selectivity of CO.sub.2 in a Polyether Block Amide Using an Electric Field

[0050] A mixture of pristine Pebax was prepared by dissolving 5 wt % of the polyether block amide Pebax 2533 purchased from Arkema in 95 wt % ethanol absolute (99-100 wt %) purchased from Merck and the mixture was stirred under reflux condition at 70° C. for 3 hours. Two samples of this mixture were prepared.

[0051] The first sample was prepared by placing an amount of the mixture on a PET support and thereafter distributed using an automatic film applicator standard purchased from TQC Sheen. The sample was allowed to stand for 20 minutes at about 22° C. thereby allowing for curing by ethanol solvent evaporation, and the resulting membrane had a uniform thickness which was 500 μm. After the solvent had evaporated the membrane was removed from the support

[0052] The second sample was prepared by placing an amount of the mixture on a PET support and thereafter distributed using an automatic film applicator standard purchased from TQC Sheen. The sample was aligned in-plane with the electrode geometry in FIG. 1 using an alternating electric field at 5 kHz, 600 V. The sample was allowed to stand for 20 minutes at about 22° C. thereby allowing for curing by ethanol solvent evaporation, and the resulting membrane had a thickness which was 500 μm. After the solvent had evaporated the membrane was removed from the support

[0053] Single gas permeability properties of the membranes were performed at 2 bar and 25° C., using a conventional constant volume/variable pressure method according to the ASTM D1434-82 standard. The gases tested in the permeability setup were pure CO.sub.2 5 (i.e. carbon dioxide gas with a purity of 99.999%), N.sub.2 5 (i.e. nitrogen gas with a purity of 99.999%), and He 4.6 (i.e. helium gas with a purity of 99.996%) all purchased from Aga AS Linde. The results are presented in Table 2 where sample 1 is the first sample, which was not subjected to an electric field, and sample 2 is the second sample, which was subjected to an electric field. It was found that the electric field increased the permeability of the CO.sub.2 through the membrane while the selectivity was maintained for CO.sub.2/N.sub.2.

TABLE-US-00002 TABLE 2 Permeability [barrer] Selectivity Sample # CO.sub.2 N.sub.2 He CO.sub.2/N.sub.2 He/N.sub.2 CO.sub.2/He 1 227 8 25 29 3 9 2 292 9 26 31 3 11

Example 3

[0054] Enhanced Permeability and Selectivity of CO.sub.2 in a Mixture of a Polyether Block Amide Polymer and a Polyethylene Polymer Using an Electric Field

[0055] A mixture of Pebax was prepared by dissolving 5 wt % of the polyether block amide Pebax 2533 purchased from Arkema in 95 wt % ethanol absolute (99-100 wt %) purchased from Merck and the mixture stirred under reflux condition at 70° C. for 3 hours. Polyethylene glycol dimethyl ether (PEGDME) Mn 250 purchased from Sigma Aldrich was added to the mixture at concentrations of 0 wt %, 30 wt %, 40 wt %, and 50 wt % and mixed by a magnetic stirrer overnight. Thereafter it was mixed in an ultrasonic bath for 1 hour. Two samples of each of these four mixtures were prepared with and without an electric field applied to it.

[0056] Samples without electric field applied were prepared by placing an amount of the mixture on a PET support and thereafter distributed using an automatic film applicator standard purchased from TQC Sheen. The sample was allowed to stand for 20 minutes at about 22° C. thereby allowing for curing by ethanol solvent evaporation, and the resulting membrane had a uniform thickness which was 500 μm. After the solvent had evaporated the membrane was removed from the support

[0057] Samples with electric field applied were prepared by placing an amount of the mixture on a PET support and thereafter distributed using an automatic film applicator standard purchased from TQXX Sheen. The sample was aligned in-plane with the electrode geometry in FIG. 1 using an electric field at 5 kHz, 600 V. The sample was allowed to stand for 20 minutes at about 22° C. thereby allowing for curing by ethanol solvent evaporation, and the resulting membrane had a uniform thickness which was 500 μm. After the solvent had evaporated the membrane was removed from the support

[0058] Single gas permeability properties of the samples were performed at 2 bar and 25° C., using a conventional constant volume/variable pressure method according to the ASTM D1434-82 standard. The gases tested in the permeability setup were pure CO.sub.2 and N.sub.2 both purchased from Aga AS Linde. The results are presented in FIG. 3A and FIG. 3B, respectively. FIG. 3A shows the CO.sub.2 permeability as a function of the amount of PEGDME in Pebax 2533. FIG. 3B shows CO.sub.2/N.sub.2 selectivity as a function as a function of the amount of PEGDME in Pebax 2533. In FIGS. 3A and 3B the term “NAL” stands for Not Aligned, i.e. no electric field was applied to the sample, and the term “IPA” stands for “In-Plane Aligned”, i.e. an electric field with in-plane geometry as indicated in FIG. 1 was applied. Further, PCO.sub.2 stands for permeability of CO.sub.2. For a given concentration of PEGDME in the membrane, the CO.sub.2 permeability was always higher in the membranes that had been prepared using an electric field compared to the membranes having been prepared in the absence of an electric field. For each of the samples, exposure to the electric field also increased the CO.sub.2/N.sub.2 selectivity. It was concluded that exposure of the membrane to an electric field with in-plane geometry increases both permeability and selectivity. This is very beneficial, as higher values are desirable for better membrane performance.

[0059] For the samples not exposed to an electric field, increasing the PEGDME concentration up to 40 wt % was found to increase CO.sub.2 permeability, whereas in concentrations above 40 wt %, the PEGDME was detrimental for the permeability. For samples exposed to an electric field, an increase in the concentration of PEGDME was accompanied by an increase in permeability, while the CO.sub.2/N.sub.2 selectivity was maintained or slightly decreased. This is believed to be the effect of the alignment of PEGDME with the electric field which may create more free volume in the bulk of the polymer chains improving the carbon dioxide permeability.

Example 4

[0060] Enhanced Permeability of a Polyether Block Amide Polymer Using an Electric Field in Dry Mixed Gas Permeability Measurements

[0061] A mixture of Pebax was prepared by dissolving 5 wt % of the polyether block amide Pebax 2533 purchased from Arkema in 95 wt % ethanol absolute (99-100 wt %) purchased from Merck and the mixture was stirred under reflux condition at 70° C. for 3 hours. Two samples of this mixture were prepared.

[0062] The first sample was prepared by placing an amount of the mixture on a PET support and thereafter distributed using an automatic film applicator standard purchased from TQC Sheen. The sample was allowed to stand for 20 minutes at about 22° C. thereby allowing for curing by ethanol solvent evaporation for 20 minutes and the resulting membrane had a thickness which was 500 μm. After the solvent had evaporated the membrane was removed from the support

[0063] The second sample was prepared by placing an amount of the mixture on a PET support and thereafter distributed using an automatic film applicator standard purchased from TQC Sheen. The sample was aligned in-plane with the electrode geometry in FIG. 1 using an electric field at 5 kHz, 600 V. The sample was allowed to stand for 20 minutes at about 22° C. thereby allowing for curing by ethanol solvent evaporation for 20 minutes and the resulting membrane had a thickness which was 500 μm. After the solvent had evaporated the membrane was removed from the support

[0064] Mixed gas permeability properties of the membranes were performed at 6 bar and 25° C., using a conventional constant volume/variable pressure method according to the ASTM D1434-82 standard. The gases tested in the permeability setup were CO.sub.2 5, N.sub.2 5, and He 4.6 all purchased from Aga AS Linde. The results are presented in Table 3. For the sample subjected to the electric field the permeability was found to increase while the selectivity was maintained or slightly increased.

TABLE-US-00003 TABLE 3 Permeability of CO.sub.2 [barrer] 10 wt % 10 wt % 45 wt % CO.sub.2 CO.sub.2 CO.sub.2 90 wt % 90 wt % 55 wt % Selectivity Sample # N.sub.2 CH.sub.4 He CO.sub.2/N.sub.2 CO.sub.2/CH.sub.4 CO.sub.2/He 1 156 145 — 49 12 — 2 161 175 280 52 14 9.3