Manufacturing method of supported carbon membrane (CM)

Abstract

The present invention relates to a method for producing a supported carbon membrane (CM), and to a method for separating a gas from a gas mixture, and to the use of the supported CM as or in a membrane reactor.

Description

[Technical field]

[0001] The present invention relates to a method for producing a supported carbon membrane (CM). The present invention also relates to a method for separating a gas from a gas mixture, to the use of the supported CM in a membrane reactor, and to its use as a membrane reactor. [Background technology]

[0002] Traditional separation methods such as distillation remain the primary processing technology accounting for 10-15% of global energy consumption. Non-thermally driven separation methods such as membranes are more efficient in terms of energy consumption, scalability, small footprint, and low environmental impact. Polymer membranes are a mature technology for water purification, but are still in the development stage for gas separation and have limitations to overcome: a) They are rarely adopted for applications above 100 °C due to lack of stability at high temperatures, which is important for processes such as CO2 capture before combustion, hydrogen separation during steam reforming from natural gas, and water-gas separation during CO2 hydrogenation for methanol synthesis. b) Polymer membranes are prone to plasticization (swelling and subsequent loss of permeability properties), such as in olefin / paraffin separation and separation of benzene derivatives from each other. c) They are subject to chemical and biochemical degradation. d) There is a trade-off between permeability and selectivity, with membranes with high permeability having low selectivity and membranes with low permeability having high selectivity. This is known as the Robson limit.

[0003] Carbon membranes (CMs) are the product of carbonization of thermosetting polymers in a non-oxidizing environment. CMs are stable at high temperatures, chemically and biochemically inert, do not plasticize, and can exceed the Robson limit. CMs have two gas separation mechanisms: molecular sieving, where gases smaller than the pores pass through, and adsorption-diffusion, where the molecules interact with the pores. The pore size, pore size distribution, and adsorption properties of the membranes can be tuned by varying the polymer precursor, carbonization temperature, carbonization time, and the addition of inorganic nanoparticles. Since the permeate rate depends on the membrane thickness, thinner membranes are desirable. However, CMs supported on a porous support are necessary because thin CMs alone (thickness less than 50 μm) lack mechanical strength.

[0004] US 2021 / 138407 discloses a method for making a supported carbon molecular sieve membrane, comprising contacting a film of a carbon-forming polymer with a polymer fabric to form a laminate, and heating the laminate to a carbonization temperature in an atmosphere and for a time sufficient to carbonize the film and polymer fabric to form a supported carbon molecular sieve membrane comprised of a separated carbon layer supported on a carbon fabric layer, wherein the film and polymer fabric are comprised of a polymer selected from the group consisting of polyvinylidene chloride copolymers, polyimides, or combinations thereof.

[0005] US Patent Publication No. 2021 / 129085 relates to a method for producing a carbon molecular sieve membrane, the method comprising the steps of providing a precursor polymer, heating the precursor polymer to a pyrolysis temperature at which the precursor polymer undergoes pyrolysis to form a carbon molecular sieve membrane, cooling the carbon molecular sieve membrane to a cooling temperature of 50°C or less, (iv) after cooling, heating the carbon molecular sieve membrane to a reheat temperature of at least 250°C and up to 400°C in a reheat atmosphere for a reheat time of 15 minutes to 48 hours, and (v) cooling the carbon molecular sieve membrane to 50°C or less.

[0006] Korean Patent Publication No. 2016-0034881 relates to a method for manufacturing a hydrogen separation membrane, which includes a step of forming a porous support, a step of forming a hydrogen separation layer on the porous support, and a step of removing surface pores of the hydrogen separation layer by thin film pressing to form a dense hydrogen separation layer and improve hydrogen selectivity.

[0007] Chinese Patent No. 109351202 relates to a method for producing a composite carbon membrane based on a ceramic tube used as a support.

[0008] The document AB Fuertes et al:”Carbon molecular sieve membranes from polyetherimide”, MICROPOROUS AND MESOPOROUS MATERIALS, ELSEVIER, AMSTERDAM, NL, Vol 26, nr. 1-3, 16 December 1998, relates to carbon molecular sieve membranes with high gas permeation selectivity for permanent gas pairs (O2-N2, N2-He, CO2-CH4) obtained by carbonization of commercial polyimides (polyetherimides). The membranes are obtained in a single casting step and consist of a thin microporous carbon membrane with a thickness of about 3 μm supported on a macroporous carbon substrate.

[0009] The article Hang Zheng Chen et al:”Multi-layer composite hollow fiber membranes derived from poly(ethylene glycol)(PEG) containing hybrid materials for CO / N separation”,JOURNAL OF MEMBRANE SCIENCE,ELSEVIER BV,Vol 381,nr.1,17 July 2011(2011-07-17),pages 211-220, is about multi-layer composite hollow fiber membranes designed by surface coating ultra-thin layers of poly(ethylene glycol)(PEG)-containing hybrid materials on polyethersulfone(PES) porous substrates for CO2 / N2 separation. Asymmetric PES hollow fiber substrates were prepared by dry-jet wet-spinning method, and multiple ultra-thin layers of PEG-containing hybrid polymers were coated on the substrates by a continuous coating device.

[0010] The literature, AKItta et al:”Effect of dry / wet-phase inversion method on fabricating polyetherimide-derived CM membrane for H2 / N2 separation”, INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, ELSEVIER, AMSTERDAM, NL, Vol 35, nr.4, 1 February 2010(2010-02-01), pages 1650-1658, is about carbon molecular sieve (CMS) membranes for hydrogen separation fabricated by casting polyetherimide (PEI) on an alumina support and using the dry / wet phase inversion method, and different coating techniques (dry method, wet method) at different pyrolysis temperatures were examined.

[0011] US Patent No. 4,840,819 relates to a method for producing a composite membrane capable of selectively passing the more permeable components of a gas mixture in a gas separation operation, comprising the steps of coating a porous support layer with a wet separation layer of membrane material and drying the separation layer on the porous support layer, the support layer containing a controlled amount of liquid in the range of about 10% to about 90% by weight of the liquid present in the support layer in a fully wetted state, the liquid being a solvent or non-solvent for the separation layer material, the presence of the liquid in the porous support layer preventing penetration of the membrane material into the pores of the porous support layer, whereby the separation layer is non-occlusive with improved permeability properties, and has a thickness of about 0.4 microns or less.

[0012] US 2011 / 030559 A1 relates to a method for producing a composite membrane comprising applying a curable composition to a porous support layer having a specific CO2 gas flux, and forming a discrimination layer on the porous support layer by curing the curable composition. The curable composition comprises a non-volatile component and optionally a volatile component, at least 60 wt% of the non-volatile component being oxyethylene groups, and the curable composition is continuously applied to the porous support layer by a production apparatus comprising a curable composition application station, an irradiation source, an irradiation device, a composite membrane recovery station, and a means for moving the porous support layer from the curable composition application station to the irradiation source and the composite membrane recovery station.

[0013] US Patent Publication No. 2018 / 133659 relates to a method of making a carbon molecular sieve membrane for industrial gas separation, the method comprising the steps of providing a porous support structure including a first major surface opposed to a second major surface defining a thickness therebetween, forming an intermediate layer including an inorganic oxide on the first major surface of the porous support structure, forming a polymer precursor film having a thickness of less than 4 μm on a surface of the intermediate layer opposed to the porous support structure, and carbonizing the polymer precursor film in an inert atmosphere at 400° C. to 750° C. to form a carbon separation layer having a thickness of less than 1 μm.

[0014] US 2014 / 199478 A1 relates to a method for producing a carbon membrane comprising the steps of immersing a porous support in a suspension of a phenolic resin or a suspension of a phenolic resin precursor, drying the support to form a membrane thereon consisting of the phenolic resin or the phenolic resin precursor, and carbonizing the membrane by heat treatment to a carbon membrane, the phenolic resin or the phenolic resin precursor being a powdered material. Summary of the Invention

[0015] The objective of the present invention is to improve the performance of CM in terms of selectivity and permeability, which makes it a great candidate for industrial gas separation and industrial applications such as a) H2 production, dehydrogenation to olefins from paraffins, H2 separation in H2 transportation and storage in gas pipelines, b) biogas upgrading, post combustion CO2 separation, c) CO2 reduction with H2 for methanol, DME, CH4 production, water and gas removal in solvent dehydration, d) separation of olefins from paraffins. The present invention therefore relates to a method for producing a supported CM, the method comprising the steps of: a) providing a porous support; b) providing a coating solution comprising a polymeric carbon precursor; c) providing a non-solvent in which the polymeric carbon precursor of b) has low solubility; d) contacting the porous support of a) with the non-solvent of c) and removing excess non-solvent from the surface of the support of a) to form a solvent-treated support; e) coating the solvent treated substrate of d) with the coating solution of b); f) drying the coated support of e); g) carbonizing the dried, coated support of f) to obtain a supported carbon membrane (CM); Equipped with. [Brief description of the drawings]

[0016] Schematic Figure 1 is an SEM schematic of a superselective CM with a top selective layer. [Figure 1] FIG. 1 shows H2 permeability at multiple temperatures for membranes fabricated with superselective CM and pore-filled CM. [Diagram 2] FIG. 1 shows N2 permeability at multiple temperatures for membranes fabricated with superselective CM and pore-filled CM. [Diagram 3] FIG. 1 shows H2 permeability at multiple temperatures for membranes fabricated with superselective CM and pore-filled CM. [Figure 4]FIG. 1 shows N2 permeability at multiple temperatures for membranes fabricated with superselective CM and pore-filled CM. [Diagram 5] FIG. 13 shows N2 permeability at multiple pressure differentials at 200° C. for membranes fabricated with superselective CM and pore-filled CM. [Figure 6] FIG. 13 shows H2 permeability at multiple pressure differentials at 200° C. for membranes fabricated with superselective CM and pore-filled CM. [Figure 7] FIG. 1 shows a comparison of H2 / N2 ideal selectivity for membranes fabricated with superselective CM and pore-filled CM. [Figure 8] FIG. 10 shows a comparison of CMSM and Robson's upper bound on H2 / N2 selectivity versus H2 permeability for polymer membranes. [Figure 9] FIG. 13 shows a comparison of CO2 permeability between pore-filled CM and superselective CM. [Figure 10] FIG. 1 shows a comparison of HO permeability as a function of temperature between pore-filled and superselective CM. [Figure 11] FIG. 10 shows a comparison of He permeability as a function of temperature in pore-filled and superselective CMs. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] Based on the above method, the object of the present invention is achieved. Furthermore, the inventors have found several advantages of this method, such as a very low resistance to gas permeation due to the structure obtained, a high porosity in the layer, no penetration of the layer into the support, an ultra-thin and uniform upper selective layer with high permeability, chemical and mechanical stability at high pressure and temperature, stable performance in the presence of CO, and stable performance in long-term permeation tests. Furthermore, the inventors have found that, due to the single-layer selective layer, no additional layers are required to enhance selectivity.

[0018] In one example, the porous support is selected from the group of inorganic supports.

[0019] In one example, the inorganic support is a ceramic metal oxide, nitride, boride, carbon or carbide, preferably selected from the group: alpha alumina, titanium oxide, zirconium oxide, ceria, gamma alumina, silicon carbide.

[0020] In another example, the porous support is a porous metal support selected from the group of stainless steel and Inconel.

[0021] In one example, the porous support is tubular.

[0022] In one example, the selective layer is deposited on the outside of the tubular support.

[0023] In one example, the coating solution b) is prepared with a thermosetting polymeric carbon precursor, such as a novolac oligomer, which is dissolved in an organic solvent, such as N-methylpyrrolidone.

[0024] In one example, step d) is performed such that the pores of the porous support of a) are filled with the non-solvent of c), and step d) is preferably performed by immersing the porous support of a) in the non-solvent of c). In step d), excess non-solvent on the porous support is removed, preferably by an absorbent cloth.

[0025] In one example, the carbonization step g) is carried out in an inert atmosphere or under vacuum, and the carbonization temperature in step g) is between 350°C and 1100°C, in particular between 450°C and 900°C, more preferably between 500°C and 850°C.

[0026] In one example, the carbonization pressure in step g) is between 2 mbar and 6 bar using multiple gases such as N2, He, Ar and air.

[0027] The present invention also relates to a supported CM that includes a selective layer on the exterior surface of the porous support. The present invention also relates to a method for separating a gas from a gas mixture, the method comprising the steps of: providing a support CM as described above or obtained according to a method for producing the support CM; providing a gas mixture comprising at least two gases; feeding a gas mixture at a temperature between 5°C and 600°C to a supporting CM to obtain a retentate and a permeate; Equipped with.

[0028] In one example, the at least two gases are selected from, but not limited to, He, HO, Ne, H2, NO, Ar, NH3, N2, O2, CO, CO2, CH4, C2H4, C2H6, propene, propane, H2S, methanol, ethanol, DME, 1-2 propanol, and 1-2 butanol. In particular, the gas mixture comprising at least two gases is selected from the group consisting of H2 / CH4, H2 / N2, H2 / CO2, CO2 / CH4, CO2 / N2, and O2 / N2.

[0029] The present invention also relates to the use of the supported CM described above or obtained according to the method for producing the supported CM as or in a membrane reactor.

[0030] In a specific embodiment, the tubular supported CM is fabricated from phenol-formaldehyde resin (novolac) by an immersion dry carbonization method, which forms a CM selective layer only on the support surface by blocking the pores on the alumina support surface with a condensable liquid, preventing the diffusion of the immersion liquid into the support pores.

[0031] CMs are synthesized by pyrolysis of thermosetting polymers such as novolac at temperatures between 350 and 1100 °C. The amorphous carbon skeleton after pyrolysis is a porous medium whose pore size can be tailored depending on the polymer properties and carbonization conditions.

[0032] Porous supports are used to enhance the mechanical stability of CMs. Alpha-alumina, titanium oxide, zirconium oxide and gamma-alumina are the most used supports for the fabrication of CMs. The thermal expansion coefficient of the support should be close to that of the CM so that cracks do not occur when heated or cooled. The performance of the fabricated CMs is analyzed using permeation tests at multiple pressures and temperatures with single gases such as H2 and N2. The ideal gas selectivity is calculated based on the permeability of a single gas through the membrane.

[0033] Scanning electron microscopy (SEM) is used to measure the thickness of the top selective layer of the CM and to calculate the gas permeability. Finally, Robson's upper limit graph is used as a benchmark for performance comparison with organic and inorganic membranes. For comparison, CMs were prepared without a non-solvent in the pores. In this case, the polymer fills the pores of the support and carbon is produced after carbonization (pore-filled CM). EXAMPLES

[0034] The precursor is synthesized by polycondensation of formaldehyde and phenol in an acidic medium to form a novolac oligomer. The process starts with melting 32 g of phenol at 50 °C in a round-bottom three-neck glass vessel. In the next step, 0.5 g of oxalic acid is added to the solution. In the final step, the temperature is increased to 85 °C and 23 g of formaldehyde (37 wt%) is added to the solution and allowed to react for 3 h. The immersion solution is prepared by dissolving the novolac oligomer in an organic solvent such as N-methyl-2-pyrrolidone. In the next step, a tubular α-alumina support (10 mm outer diameter, 7 mm inner diameter) was used. One end was closed and both end faces were sealed with glass to glass leaving an effective membrane length of xx cm. The porous support was immersed in a non-solvent and the pores were filled with the solution. The excess non-solvent present on the surface is removed with absorbent paper. The support is then dip-coated with the prepared polymer solution in a custom-made immersion machine. After dip coating, the coated substrate is transferred to a rotary drying oven and dried for 24 hours at 80° C. In the final step, the coated substrate is transferred to a carbonization furnace and carbonized at 600° C. under an inert atmosphere.

[0035] After carbonization, the membrane is used in a test permeation device. The presence of an aqueous solution in the pores of the support prevents the polymer from diffusing into the support. Since the polymer is not soluble in the non-solvent, it precipitates at the mouth of the pores. This phenomenon results in a thin upper selective layer CM in one immersion-drying-carbonization step. If the pores are not clogged with non-solvent, the immersion solution containing the polymer will diffuse into the pores, resulting in a smaller pore size after carbonization and a higher resistance to the passage of the permeating gas. Moreover, several immersion-carbonization steps are required to form a continuous, defect-free selective layer.

[0036] After carbonization, the membrane is used in a permeation cell for testing. The presence of an aqueous solution in the pores of the support prevents the immersion liquid from diffusing into the support. This phenomenon forms an upper selective layer CM.

[0037] Single gas permeation tests are performed at a pressure difference between the permeate and reflux liquid in the range of 1-6 and at temperatures in the range of 45-200°C. The ideal gas selectivity is calculated based on the permeability of H2 and N2 through the membrane, and the ratio is considered as the ideal selectivity. Figure 7 shows a comparison of the H2 / N2 ideal selectivity of membranes prepared by superselective CM and pore-filled CM.

[0038] H2 permeability measurements at temperatures between 45 and 200 °C were carried out with a pressure difference between the permeate and reflux of 1 to 6 bar. Figures 3 and 4 show the effect of this method on the performance of the CM in terms of H2 and N2 permeability versus temperature.

[0039] To analyze the defects present in the CM, multiple pressure difference tests of the CM were performed. As can be seen in Figures 5 and 6, the slopes of H2 and N2 permeability versus pressure are zero for both the superselective CM and the pore-filled CM, indicating that the CM is defect-free.

[0040] In this way, both the selectivity and permeability of CM are improved, making this membrane separation technology competitive for separating and purifying gases such as H2 at industrial scale in ammonia production, power generation, metal refining, etc. Figure 8 shows a comparison of the CM and Robson upper limit values ​​of H2 / N2 selectivity vs. H2 permeability of the polymer membranes.

[0041] When comparing the performance of CM with the upper limit performance of polymer membranes, both pore-filled CM and superselective CM showed higher performance than polymer membranes in H2 / N2 selectivity and H2 permeability. Superselective CM also shows higher performance than CMSM with micropores under the same operating conditions such as pressure and temperature. The features of the superselective CM of the present invention include i) ultrathin and defect-free selective layer, ii) extremely high permeability with high selectivity, iii) blocking of pores in the support pair to prevent diffusion, and iv) top selective layer membrane instead of pore-filled membrane.

[0042] The fabrication (superselective) of carbon membranes (CMs) was investigated and compared with pore-filled CMSMs in several separation processes.

[0043] This method was tested for the separation of CO2 from CH4 for applications in natural gas purification and steam reforming. The permeance of CM prepared by this method was compared with that of pore-filled membranes, as shown in Fig. 9.

[0044] As seen in Fig. 9, the superselective CMs prepared by this method exhibited higher CO2 permeability at operating temperatures between 20 and 350 °C. The higher CO2 permeability in the new membranes indicates the potential of this innovation to adapt CMs for industrial applications such as post-combustion CO2 removal by reducing the surface area required for separation.

[0045] In another study on the superior performance of superselective CM, separation of water under reaction conditions was investigated and the H2O permeability of the pore-filled CM was compared with the novel CM. Water is produced as a by-product in many reactions such as methanol synthesis. By in situ separation of water from the reaction environment, the production of the desired product such as methanol can be increased due to the shift of the equilibrium based on the Le Châtelier effect. Increasing the H2O permeability of the membrane developed to operate at temperatures up to 400 °C allows the integration of separation and reaction into one unit, which results in an improved process yield. The fabrication of the superselective CM was carried out with the aim of improving the H2O permeability at high operating temperatures. The results are summarized in Figure 10. As shown in Figure 10, the present CM showed higher performance in H2O permeability than the pore-filled CM at all operating temperatures (120-400 °C).

[0046] Compared with pore-filled CM, the novel method has better control over the pore size distribution and selective layer thickness, and therefore the performance of CM was improved in terms of permeation selectivity to separate helium gas from natural gas. Helium is a rare gas produced only from the separation and purification process of natural gas. The United States is the world's leading producer of helium, and its price has tripled in the past six years due to the scarcity of this element and its important role in industries such as pharmaceuticals, aerospace, and healthcare. Efficient separation of helium from methane can significantly reduce the final cost of pure helium and increase the helium production from dilute gas wells with dilute helium concentrations. CM with narrow pore size distribution was produced by the present method, and helium permeation tests were performed at low temperatures. Figure 11 shows the performance of CM in terms of helium permeability as a function of CM temperature. The superselective CM has a helium permeability of 398 mol.m at an operating temperature of 20 °C. -2 .s -1 .Pa -1 .e -8 The pore-filled membrane reached 232 mol.m -2 .s -1 .Pa -1 .e -8The higher the helium permeability, the smaller the surface area required, resulting in lower CAPEX and OPEX for the separator.

[0047] The present invention can be used in industries requiring the production and purification of pure gases, such as CO2 separation and utilization, hydrogen recovery from waste, hydrogen production, hydrogen refining, hydrogenation and dehydrogenation chemical reactions, etc. Companies using the present invention include, but are not limited to, ammonia production for hydrogen purification and separation from off-gas, metal refineries for hydrogen and CO recovery from blast furnaces, power plants for pre-combustion operations, oil refineries for heavy oil hydrogenation, petrochemical plants for dehydrogenation in polymer production, biorefineries for hydrogenation, biosyngas production for hydrogen and CO purification and recovery, He separation from natural gas, natural gas sweetening, biogas upgrading, H2S separation from biogas, N2 separation from natural gas, etc.

Claims

1. a) providing a porous support; b) providing a coating solution comprising a polymeric carbon precursor; c) providing a non-solvent in which the polymeric carbon precursor of b) has low solubility; d) contacting the porous support of a) with the non-solvent of c) and removing excess non-solvent from the surface of the porous support of a) to form a solvent-treated support; e) coating the solvent treated substrate of d) with the coating solution of b); f) drying the coated substrate of e); g) carbonizing the dried, coated support of f) to obtain a supported carbon membrane (CM); A method for producing a supported carbon membrane (CM) comprising:

2. The method for producing a supported carbon membrane (CM) according to claim 1, wherein the porous support is selected from the group comprising inorganic supports.

3. 3. The method for producing a supported carbon membrane (CM) according to any one or more of claims 1 to 2, wherein the inorganic porous support is a metal oxide, nitride, boride, carbon or carbide based ceramic, preferably selected from the group of alpha alumina, titanium oxide, zirconium oxide, ceria and gamma alumina silicon carbide.

4. The method for producing a supported carbon membrane (CM) according to any one or more of claims 1 to 2, wherein the porous support is a metal selected from the group consisting of steel, stainless steel, and Inconel.

5. The method for producing a supported carbon membrane (CM) according to any one or more of claims 1 to 4, wherein the coating solution of step b) is prepared by a thermosetting polymeric carbon precursor, such as a novolac oligomer, and the thermosetting polymeric carbon precursor is dissolved in an organic solvent, such as N-methylpyrrolidone.

6. The method for producing a supported carbon membrane (CM) according to any one or more of claims 1 to 5, wherein step d) is carried out such that the pores of the porous support of a) are filled with the non-solvent of c).

7. The method for producing a supported carbon membrane (CM) according to any one or more of claims 1 to 6, wherein step d) is carried out by immersing said porous support of a) in said non-solvent of c).

8. The method for producing a supported carbon membrane (CM) according to any one or more of claims 1 to 7, wherein in step d) excess non-solvent on the porous support is removed with an adsorbent cloth.

9. Method for producing a supported carbon membrane (CM) according to any one or more of claims 1 to 8, wherein the carbonization step g) is carried out in an inert atmosphere or under vacuum.

10. The method for producing a supported carbon membrane (CM) according to any one or more of claims 1 to 9, wherein in step g) the carbonization temperature is between 350°C and 1100°C, preferably between 450°C and 900°C, more preferably between 500°C and 850°C.

11. In step g), N ２ 11. The method for producing a supported carbon membrane (CM) according to any one or more of claims 1 to 10, wherein the carbonization pressure with multiple gases such as He, Ar and air is 2 mbar to 6 bar.

12. A supported carbon membrane (CM) comprising a selective layer on the outer surface of a ceramic support.

13. Providing a supported carbon membrane (CM) according to claim 12 or obtained according to any one or more of claims 1 to 11; providing a gas mixture comprising at least two gases; supplying said gas mixture to said supporting carbon membrane (CM) at a temperature between 5° C. and 600° C. to obtain a retentate and a permeate; 1. A method for separating a gas from a gas mixture comprising:

14. The at least two gases are He, H ２ O, Ne, H ２ , NO, Ar, NH ３ , N ２ , O ２ , CO, CO ２ , C.H. ４ , C ２ H ４ , C ２ H ６ , Propene, Propane, H ２ S, methanol, ethanol, DME, 1-2 propanol and 1-2 butanol, and in particular, the gas mixture containing said at least two gases is selected from He / CH ４ , H ２ S / CH ４ , H ２ / CH ４ , H ２ / N ２ , H ２ / CO ２ , CO ２ / CH ４ , CO ２ / N ２ , and O ２ / N ２ 13. The method for separating a gas from a gas mixture according to claim 12, wherein the gas is selected from the group consisting of:

15. Use of a supported carbon membrane (CM) according to claim 12 or obtained according to any one or more of claims 1 to 11 as or in a membrane reactor.

16. H ２ Production of olefins from paraffins by dehydrogenation, H in gas pipes ２ H in the transportation and storage of ２ Separation; Biogas upgrading, post-combustion CO ２ Separation of methanol, DME, CH ４ For the manufacture of H ２ CO ２ Use of the supported carbon membrane (CM) according to claim 12 or obtained according to any one or more of claims 1 to 11 as a CM in industrial gas separations and industrial applications selected from the group comprising: reduction, removal of water, gases in solvent dehydration; separation of olefins from paraffins.

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