Technical Field

The present invention relates to a palladium-based membrane and a method of forming the same.

Background

Lighter alkenes are the important building blocks of an enormous range of chemicals and polymers in different industries. Propene is one of the major lighter alkenes which is used for production of poly-propene, acrylonitrile etc. Conventional steam cracking of higher hydrocarbons, such as naphtha and other by-products of oil industry is the widespread means for producing propylene. Catalytic propane dehydrogenation is one of the major technique for production of propene on a larger scale. The reaction is highly endothermic and requires a high temperature. Mostly, the catalytic conversion of the reaction is equilibrium controlled and thus, the removal of either propene or hydrogen during the reaction could increase the conversion of the reaction. Therefore, hydrogen permeable membranes such as palladium (Pd) membranes have been used for lighter alkane dehydrogenation processes to simultaneously and selectively remove the in situ produced hydrogen from the reaction.

However, Pd membranes are not very stable in the presence of contaminating gases like hydrocarbons. Particularly in the presence of unsaturated hydrocarbons like propene, hydrogen permeation flux decreases drastically in the Pd membranes. The hydrocarbon species gets absorbed on the surface of Pd membrane and the membrane surface gets contaminated with deposited carbon. This blocks the active sites for dissociative chemisorption of hydrogen and accordingly, decreases the hydrogen permeation flux.

To overcome this, zeolite covered Pd membranes have been used in which a zeolite layer with uniform pore size is formed directly on the Pd layer on the membrane surface so as to restrict the hydrocarbons and improve membrane stability. However, due to increased mass transfer resistance and covering of zeolite over Pd layer on the membrane surface, there is a drastic reduction in hydrogen permeation loss as compared to a bare Pd membrane.

Thus, there is a need for an improved Pd-based membrane. Summary of the invention

The present invention seeks to address these problems, and/or to provide an improved Pd-based membrane.

According to a first aspect, the present invention provides a membrane comprising: - a porous support layer having a first surface and a second surface; a palladium (Pd)-based selective layer on a first surface of the support layer; and a zeolite protective layer on a second surface of the support layer, wherein the support layer is between the Pd-based selective layer and the zeolite protective layer.

The membrane may be suitable for use in hydrogenation/dehydrogenation reaction or reforming reactions.

The porous support layer may be any suitable support layer. According to a particular aspect, the support layer may comprise a ceramic material. The ceramic material may be any suitable ceramic material, comprising, but not limited to: alumina, titania, zirconia, yttria, ceria, or a combination thereof. In particular, the support layer may comprise alumina.

The porous support layer may comprise pores. According to a particular aspect, the support layer may comprise pores each having an average pore size of 50-200 nm.

The support layer may be in any suitable form. For example, the support layer may be, but not limited to, a hollow fibre support layer, a tubular support layer, or a disc.

According to a particular aspect, the support layer may be a hollow fibre support layer having an inner circumferential surface and an outer circumferential surface and wherein the palladium (Pd)-based selective layer is provided on the inner circumferential surface and the zeolite protective layer is provided on the outer circumferential surface. The hollow fibre support layer may have a suitable outer diameter. For example, the outer diameter of the support layer may be 800-4000 pm. The hollow fibre support layer may have a suitable inner diameter. For example, the inner diameter of the support layer may be 500-2000 pm. The Pd-based selective layer may be any suitable Pd-comprising selective layer. According to a particular aspect, the selective layer may comprise palladium or a palladium alloy. For example, the palladium alloy may be, but is not limited to, palladium-silver alloy, palladium-silver-copper alloy, palladium-silver-cobalt alloy, palladium-copper alloy, palladium-nickel alloy, palladium-gold alloy, palladium-gold- cobalt alloy, palladium-gold-iridium alloy, palladium-gold-rhodium alloy, palladium- ruthenium alloy, or a combination thereof.

The Pd-based selective layer may have a suitable thickness. For example, the Pd- based selective layer may have a thickness of 0.5-5.0 pm. The zeolite protective layer may be any suitable zeolite-comprising layer. According to a particular aspect, the zeolite protective layer comprises aluminosilicate zeolite. For example, the aluminosilicate zeolite may be, but not limited to, Linde type A (LTA) zeolite, H-sodalite (H-SOD) zeolite, titanium silicalite-1 zeolite, zeolite Socony Mobil-5 (ZSM-5), or a combination thereof. The zeolite protective layer may have a suitable thickness. For example, the zeolite protective layer may have a thickness of 0.5-3.0 pm.

According to a particular aspect, the membrane may further comprise a catalyst layer on the zeolite protective layer. The catalyst layer may comprise metal nanoparticles. In particular, the catalyst may comprise Ni-based nanoparticles. According to a second aspect, there is provided a method of preparing a membrane, the method comprising: forming a palladium (Pd)-based selective layer on a first surface of a porous support layer; and forming a zeolite protective layer on a second surface of the porous support layer, wherein the porous support layer is between the Pd-based selective layer and the zeolite protective layer.

According to a particular aspect, the forming a Pd-based selective layer may comprise forming the Pd-based selective layer by any suitable method. For example, the forming a Pd-based selective layer may comprise, but is not limited to, electroless plating the Pd-based selective layer on the first surface of the support layer.

The Pd-based selective layer may be any suitable Pd-based selective layer. According to a particular aspect, the Pd-based selective layer may be a Pd-based selective layer as described above in relation to the first aspect.

The forming a zeolite protective layer may comprise forming the zeolite protective layer by any suitable method. For example, the forming a zeolite protective layer may comprise, but is not limited to, coating the zeolite protective layer on the second surface of the support layer by secondary growth hydrothermal method. The zeolite protective layer may be any suitable zeolite layer. According to a particular aspect, the zeolite protective layer may be a zeolite protective layer as described above in relation to the first aspect.

The method may further comprise forming a support layer prior to the forming a Pd- based selective layer. The forming a support layer may be by any suitable method. For example, the forming a support layer may comprise, but is not limited to, forming the support layer by phase inversion.

The porous support layer may be any suitable support layer. According to a particular aspect, the porous support layer may be a support layer as described above in relation to the first aspect. The method may further comprise forming a catalyst layer on the zeolite protective layer. The catalyst layer may be formed by any suitable method. For example, the catalyst layer may be formed by hydrothermal synthesis.

The catalyst layer may be any suitable catalyst layer. According to a particular aspect, the catalyst layer may be a catalyst layer as described above in relation to the first aspect.

Brief Description of the Drawings

In order that the invention may be fully understood and readily put into practical effect there shall now be described by way of non-limitative example only exemplary embodiments, the description being with reference to the accompanying illustrative drawings. In the drawings: Figure 1 shows a schematic representation of a membrane according to one embodiment of the present invention;

Figure 2(a) shows SEM image of surface of Pd-based selective layer of membrane M1, Figure 2(b) shows SEM image of surface of zeolite protective layer of membrane M1, Figure 2(c) shows SEM image of cross-section of Pd-based selective layer of membrane M1, and Figure 2(d) shows SEM image of cross-section of zeolite protective layer of membrane M 1 ;

Figure 3(a) shows SEM image of surface of Pd-based selective layer of membrane M2, Figure 3(b) shows SEM image of surface of zeolite protective layer of membrane M2, Figure 3(c) shows SEM image of cross-section of Pd-based selective layer of membrane M2, and Figure 3(d) shows SEM image of cross-section of zeolite protective layer of membrane M2;

Figure 4(a) shows SEM image of surface of Pd-based selective layer of membrane M3, Figure 4(b) shows SEM image of surface of zeolite protective layer of membrane M3, Figure 4(c) shows SEM image of cross-section of Pd-based selective layer of membrane M3, and Figure 4(d) shows SEM image of cross-section of zeolite protective layer of membrane M3;

Figure 5(a), 5(b) and 5(c) show the XRD pattern of membranes M1, M2 and M3, respectively; Figure 6 shows effect of contaminants on hydrogen permeation in M1 membrane;

Figure 7 shows stability test of membrane M1 for hydrogen purification using 10% C3H8 and C3H6 in hydrogen for 72 hours;

Figure 8 shows the effect of contaminants on hydrogen permeation in membrane M4;

Figure 9(a) shows the SEM image of membrane M1, Figure 9(b) shows the SEM image of membrane M4 and Figure 9(c) shows the SEM image of filamentous carbon deposit on the surface of membrane M4, after being exposed to C3H8 at 600°C;

Figure 10(a) shows TGA of spent membrane M4 and Figure 10(b) shows the TGA of spent membrane M1 after exposure to C3H8 and C3H6; Figure 11 shows hydrogen separation performance of the membranes M1, M2 and M3 according to embodiments of the present invention as compared to membrane M4 in presence of 10% C3H6 and 10% C3H8;

Figure 12 shows the SEM image of a membrane M5 according to one embodiment of the present invention;

Figure 13 shows comparison of performance of membranes M3 and M5 in presence of C3H6 and C3H8;

Figure 14(a) shows propane dehydrogenation in a FBR reactor and Figure 14(b) shows a triple layer CMR using 7% Cr/AhC catalyst (under reaction condition: 200 mg catalyst, 10% C3H8 in He and 600°C);

Figure 15 shows hydrogen permeation in a tubular membrane according to one embodiment of the present invention (Reaction conditions: gas composition= 80% H2, 10% C3H6 and 10%C3H ₈ , T = 600°C, P = 1 bar pressure, N ₂ sweep gas);

Figure 16 shows a schematic representation of coupling endothermic PDH reaction with exothermic C0 ₂ methanation reaction in a catalytic membrane reactor comprising a membrane according to one embodiment of the present invention;

Figure 17(a) shows the performance of a bi-functional membrane reactor during PDH reaction, and Figure 17(b) shows the performance of the reactor during CO2 methanation reaction; Figure 18 shows a schematic representation of a reactor comprising a membrane comprising a modified zeolite protective layer (i.e. catalyst layer and zeolite protective layer) according to one embodiment of the present invention;

Figure 19 shows a schematic representation of a process of forming a membrane comprising a modified zeolite protective layer according to one embodiment of the present invention;

Figure 20(a) shows the SEM image of a membrane according to one embodiment of the present invention, Figure 20(b) shows the SEM image of an unmodified zeolite protective layer of the membrane, Figure 20(c) shows the SEM image of an modified zeolite protective layer of the membrane, and Figure 20(d) shows the cross section of the outer layer of the membrane following modification of the zeolite protective layer;

Figure 21 shows the hydrogen flux performance of two different membranes according to the present invention; Figure 22 shows CFU decomposition reaction in a Ni-PS modified membrane reactor. Detailed Description

As explained above, there is a need for an improved palladium (Pd)-based membrane, particularly one which can be used for effective separation of hydrogen from different feed stocks. In general terms, the present invention provides a triple layered membrane. The membrane may comprise a support layer with a homogeneous layer of zeolite and a palladium-based material on either side of the support layer. The membrane of the present invention may comprise improved thermal and chemical stability. In particular, the membrane may improve the poisoning of Pd-based membranes in the presence of hydrocarbons and other coke forming agents, particularly when used in hydrogen recovery applications.

According to a first aspect, the present invention provides a membrane comprising: a porous support layer having a first surface and a second surface; a palladium (Pd)-based selective layer on a first surface of the support layer; and a zeolite protective layer on a second surface of the support layer, wherein the support layer is between the Pd-based selective layer and the zeolite protective layer. The membrane may be suitable for use in any suitable application. For example, the membrane may be used in hydrogenation/dehydrogenation reactions or reforming reactions such as, but not limited to, hydrocarbon reforming reactions. Other suitable applications include, but not limited to, propane dehydrogenation, carbon dioxide hydrogenation, hydrocarbon reforming for hydrogen production and carbon dioxide reforming of methane. In particular, the coke resistant properties of the membrane enable its use in dehydrogenation reactions. The membrane comprising the zeolite protective layer enables the membrane to effectively recover hydrogen during dehydrogenation reactions, thereby surpassing the thermodynamic limitations and moving the equilibrium towards more product formation.

The membrane according to the present invention, by comprising a Pd-based selective layer and a zeolite protective layer on either side of a support layer enables the selective layer and the protective layer to homogeneously and strongly adhere to the surface of the support layer.

The porous support layer may be any suitable support layer. The support layer may comprise any suitable material. For example, the support layer may comprise an inorganic material. The inorganic material may be, but not limited to, alumina, alumina- YSZ, ceramic, stainless steel, vycor glass, or a combination thereof. According to a particular aspect, the support layer may comprise a ceramic material. The ceramic material may be any suitable ceramic material, comprising, but not limited to: alumina, titania, zirconia, yttria, ceria, or a combination thereof. In particular, the support layer may comprise alumina.

The porous support layer may comprise pores having a suitable pore size. According to a particular aspect, the support layer may comprise pores having an average pore size of 50-200 nm. In particular, the support layer may comprise pores having an average pore size of 75-175 nm, 100-150 nm, 110-125 nm. Even more in particular, the average pore size may be about 50 nm.

The support layer may be in any suitable form and shape. For example, the support layer may be, but not limited to, a hollow fibre support layer, a tubular support layer, or a disc. According to a particular aspect, the support layer may be a hollow fibre support layer. According to a particular aspect, the support layer may be a hollow fibre support layer having an inner circumferential surface and an outer circumferential surface and wherein the palladium (Pd)-based selective layer is provided on the inner circumferential surface and the zeolite protective layer is provided on the outer circumferential surface. The hollow fibre support layer may have a suitable outer diameter. For example, the outer diameter of the support layer may be 800-4000 pm. In particular, the outer diameter may be 1000-3800 pm, 1200-3500 pm, 1500-3300 mm, 1800-3000 mm, 2000- 2800 mm, 2200-2500 mm. Even more in particular, the outer diameter may be about 1800 pm.

The hollow fibre support layer may have a suitable inner diameter. For example, the inner diameter of the support layer may be 500-2000 pm. In particular, the inner diameter may be 750-1750 pm, 900-1500 pm, 1000-1400 pm, 1100-1300 pm, 1200- 1250 pm. Even more in particular, the inner diameter may be about 1400 pm.

The Pd-based selective layer may be any suitable Pd-comprising selective layer. The Pd-based selective layer may comprise palladium in any suitable form. For example, the Pd-based selective layer may comprise palladium or a palladium alloy. According to a particular aspect, the palladium alloy may be, but is not limited to, palladium-silver alloy, palladium-silver-copper alloy, palladium-silver-cobalt alloy, palladium-copper alloy, palladium-nickel alloy, palladium-gold alloy, palladium-gold-cobalt alloy, palladium-gold-iridium alloy, palladium-gold-rhodium alloy, palladium-ruthenium alloy, or a combination thereof.

The Pd-based selective layer may have a suitable thickness. For example, the Pd- based selective layer may have a thickness of 0.5-5.0 pm. In particular, the thickness of the Pd-based selective layer may be 0.7-4.8 pm, 0.8-4.5 pm, 1.0-4.3 pm, 1.2-4.0 pm, 1.5-3.8 pm, 1.7-3.5 pm, 2.0-3.2 pm, 2.2-3.0 pm, 2.5-2.8 pm. Even more in particular, the thickness may be about 1.0 pm.

The zeolite protective layer may be any suitable zeolite-comprising layer. The zeolite protective layer may comprise any suitable zeolite. According to a particular aspect, the zeolite protective layer may comprise an aluminosilicate zeolite. For example, the zeolite protective layer may comprise, but is not limited to, Linde type A (LTA) zeolite, H-sodalite (H-SOD) zeolite, titanium silicalite-1 zeolite, zeolite Socony Mobil-5 (ZSM-5), or a combination thereof.

The zeolite protective layer may have a suitable thickness. For example, the zeolite protective layer may have a thickness of 0.5-3.0 pm. In particular, the thickness may be 0.7-2.8 pm, 0.8-2.5 pm, 1.0-2.3 pm, 1.2-2.0 pm, 1.5-1.8 pm. Even more in particular, the thickness may be about 1.0 pm. The zeolite protective layer may be functionalised. For example, the zeolite protective layer may be functionalised in any suitable manner. In particular, the zeolite protective layer may be functionalised by catalytic material. Even more in particular, the zeolite protective layer may be functionalised by active metals by forming phyllosilicate structures.

Accordingly, the membrane may further comprise a catalyst layer on the zeolite protective layer. The catalyst layer may provide active catalytic centres when the membrane is in use, such as in use during pyrolysis reactions. The catalyst layer may be any suitable catalyst layer. For example, the catalyst layer may comprise metal nanoparticles. In particular, the catalyst may comprise Ni-based nanoparticles. Even more in particular, the Ni-based nanoparticles may comprise, but not limited to, Ni-Cu, Ni-Co, Ni-Pt, or a combination thereof. The zeolite protective layer and the catalyst layer form a modified zeolite protective layer. The modified zeolite protective layer acts as both a catalyst when the membrane is used in hydrogenation/dehydrogenation and reforming reactions and as a protective layer for the membrane. Accordingly, in use, the membrane enables catalyses of the reactions, increase in hydrogen flux through the membrane by inhibiting coke formation on the membrane and at the same time, increase yield of the reaction by selectively removing hydrogen.

According to a particular embodiment, there is provided a hollow fibre membrane comprising: a porous hollow fibre support layer; a Pd-based selective layer on an inner circumferential surface of the hollow fibre support layer; and a zeolite protective layer on an outer circumferential surface of the hollow fibre support layer. In particular, providing a zeolite protective layer on the outer side of the hollow fibre membrane provides the membrane with an prolonged life due to reduction in coke deposition when the membrane is used in dehydrogenation reactions. A schematic representation of one embodiment of a hollow fibre membrane according to the present invention is as shown in Figure 1.

The present invention also provides a method of forming a Pd-based membrane. According to a second aspect, there is provided a method of preparing a Pd-based membrane, the method comprising: forming a palladium (Pd)-based selective layer on a first surface of a porous support layer; and forming a zeolite protective layer on a second surface of the porous support layer, wherein the porous support layer is between the Pd-based selective layer and the zeolite protective layer.

The porous support layer may be any suitable porous support layer. According to a particular aspect, the support layer may be a support layer as described above in relation to the first aspect.

The Pd-based selective layer may be any suitable Pd-based selective layer. According to a particular aspect, the Pd-based selective layer may be a Pd-based selective layer as described above in relation to the first aspect.

The forming a Pd-based selective layer on a first surface of a porous support layer may be by any suitable method. For example, the forming may comprise, but is not limited to, electroless plating the Pd-based selective layer on the first surface of the support layer.

The zeolite protective layer may be any suitable zeolite layer. According to a particular aspect, the zeolite protective layer may be a zeolite protective layer as described above in relation to the first aspect.

The forming a zeolite protective layer on a second surface of the porous support layer may comprise forming the zeolite protective layer by any suitable method. For example, the forming a zeolite protective layer may comprise, but is not limited to, coating the zeolite protective layer on the second surface of the support layer. In particular, the coating may be by secondary growth hydrothermal method.

The method may further comprise forming a support layer prior to the forming a Pd- based selective layer. The forming a support layer may be by any suitable method. For example, the forming a support layer may comprise, but is not limited to, phase inversion.

The method may further comprise forming a catalyst layer on the zeolite protective layer following the forming a zeolite protective layer on a second surface of the porous support layer. The catalyst layer may be formed by any suitable method. For example, the catalyst layer may be formed by hydrothermal synthesis. The catalyst layer may be any suitable catalyst layer. According to a particular aspect, the catalyst layer may be a catalyst layer as described above in relation to the first aspect.

Having now generally described the invention, the same will be more readily understood through reference to the following example which is provided by way of illustration, and is not intended to be limiting.

Examples

Example 1

Preparation of membranes Three different Pd-based membranes were formed. In particular, the three zeolite protected Pd-based membranes were named: M1 (LTA outside, Pd inside of AI ₂ O ₃ hollow fibre); M2 (H-SOD outside, Pd inside of AI ₂ O ₃ hollow fibre); and M3 (TS-1 outside, Pd inside of AI ₂ O ₃ hollow fibre).

The alumina substrate surface had asymmetric pores on both side of the substrate for better adherence and homogeneity in coating the zeolites and the Pd layer.

Additionally, another membrane, membrane M4, was also prepared using conventional method for providing a basis of comparison. Membrane M4 was an unprotected Pd- based membrane.

The alumina hollow fibre substrate had the following dimensions: 200 mm length, 2 mm outer diameter (OD), 1.6 mm inner diameter (ID), 100 nm average pore size. The detailed experimental procedure for membrane preparation is given below. The a- alumina hollow-fibre used was synthesized by phase inversion method. The calcined hollow fibres were thoroughly cleaned in 1 M nitric acid (HNO ₃ ) for 4 hours followed by washing in Dl water. Two different layers were deposited on either side of the a-alumina hollow-fibre substrate using different techniques. The inner circumferential surface was coated with a Pd layer using electroless plating method and the outer circumferential layer was coated with a zeolite layer using a secondary growth hydrothermal technique. Prior to electroless deposition, the substrate inner surface was seeded by two-step sensitization/activation process. The process was carried out using acidic solution of SnCI ₂ (3.7 g/L) and PdCI ₂ (0.88 g/L) solution. The outer surface of the substrate was protected using Teflon and the two solutions were flown inside the tube using a peristaltic pump (Masterflex® L/S® Digital drive). The process was repeated for 10 times and the substrate was cleaned with Dl water followed by oven drying.

(i) Pd-based selective layer formation

The activated substrate was then subjected to electroless deposition using hydrazine based plating baths. The plating solution was prepared by dissolving 0.2 g of PdCI ₂ into 18 ml NH ₄ OH in 82 ml water under ultrasonic condition, further 3.8 g of Na2EDTA was added to this and stirred for 30 min until a clear solution appeared. The solution was preheated to 60°C in a water bath and recirculated inside the activated hollow fibre substrate. Hydrazine was added batch wise to the plating solution and the pH was also adjusted with time adding drops of NH ₄ OH. After Pd deposition the membrane was cleaned in Dl water until the pH became about 7 and dried at 100°C overnight.

(ii) Zeolite protective layer formation

The zeolite layer was coated using secondary growth method, where, the outer layer of the substrate was seeded with zeolite seeds and the layer was then grown under hydrothermal treatment. For membrane M1, LTA-zeolite was coated on the outer surface of inner coated Pd- membrane after capping both ends with Teflon. The zeolite membrane/seeds were deposited using a synthesis solution in a molar ratio of 50 Na ₂ 0:1 AI ₂ C> ₃ :5 H ₂ 0:1000 H ₂ 0. 22.22 gm of NaOH was added to 100 ml of water followed by dissolving 1.147g of sodium aluminate (NaAI0 ₂ ) and the solution was stirred for 30 min for complete dissolution. 4.825 ml of sodium silicate solution was added drop wise to the aluminate solution under vigorous stirring conditions. The solution was stirred for 4 hours to form a transparent gel. For the seed preparation, the gel was put inside a Teflon liner inside a stainless steel autoclave and hydrothermal treatment was carried out for 24 hours at 60°C. The formed LTA zeolite was collected by centrifuge method, and particle size above 200 pm size was sieved out. Zeolite particles of £ 200 pm size were used as the seed. The cleaned substrate was seeded by dip coating method using 10 wt % zeolite water suspension. The process was repeated for 4-5 times with intermediate drying at 373 K for 1 hour. Finally, the seeded substrate was put inside an autoclave containing freshly prepared gel of similar composition as mentioned above and treated under hydrothermal at 60°C for 24 hours.

The membrane was then taken out and cleaned thoroughly with deionized water several times to remove any unreacted base or silica residue. The membrane was finally dried overnight at 100°C and used for hydrogen purification experiments.

For the preparation of membranes M2 and M3, a similar approach as was used for membrane M1 was used but under different experimental conditions.

For membrane M2, for the H-SOD deposition, the gel composition was similar to that of LTA in membrane M1 (50 Na ₂ 0:1 Al ₂ C> ₃ :5 H ₂ q:1000 H2O), but the hydrothermal temperature was 140°C for 4 hours.

For the preparation of membrane M3, for the TS-1 zeolite deposition, the gel composition was 1TEOS: 0.01 TBOT:0.18 TPAOH: 250 H2O and the hydrothermal temperature was 160°C for 24 hours. Characterization of membranes

The morphology of the membranes were characterized by scanning electron microscope (SEM) using SEM, JEOL2872. The formation of zeolite and zeolite membrane was characterized by X-ray diffraction analysis using a Rigaku XRD equipped with Cu-K(a) radiation source operated at 40 kV and 30 mA current. The SEM images of membranes M1, M2 and M3 are as shown in Figures 2 to 4, respectively. The SEM image of membrane M1 as shown in Figure 2(b) showed that the zeolite protective layer formed on the outer circumferential surface of the alumina substrate was homogeneous and defect free. The Pd-based selective layer formed on the inner circumferential surface of the alumina substrate was also homogeneous and defect free and was about 1 mhi thick, as seen in Figure 2(a). The formation of LTA crystals was confirmed from the cubical and sharp edges of the zeolite protective layer surface. The crystal structure was also further conformed from the XRD analysis and matched.

Figures 3 and 4 also depict the deposition of the zeolite protective layer on the outer circumferential side and the Pd-based selective layer on the inner circumferential side of the hollow fiber substrates of membranes M2 and M3. In particular, formation of H- SOD protective layer in membrane M2 on the outer circumferential side of the hollow fibre substrate was evident from the spherical rice ball like structure in the SEM image in Figure 3(b). Similarly, formation of the TS-1 zeolite protective layer was confirmed from the SEM analysis of membrane M3, which showed hexagonal crystals grown on the alumina substrate (see Figure 4(b)).

The cross-sectional SEM images of the three membranes showed pore filled plating, and that the membranes had penetrated well inside the asymmetric hollow fibre pores. This increased the adherence properties of the zeolite protective layer and the Pd- based selective layers with the alumina support layer, enabling the membranes to become resistant to thermal cycling.

From Figures 5(a) to (c) showing the XRD patterns of the three respective zeolite protective layers of membranes M1, M2 and M3, it was further confirmed that crystalline zeolite protective layers had indeed formed on the outer circumferential surface of the alumina support layer.

Use of the membranes

Membrane M1 was tested for hydrogen (H ₂ ) permeation under different conditions and at temperatures up to 600°C, which is considered an ideal temperature for propane dehydrogenation and different reforming reactions such as C0 ₂ reforming of methane and steam reforming of toluene. The H ₂ permeation for membrane M1 as a function of temperature under different gas feed conditions is provided in Figure 6.

The hydrogen permeation flux increased with an increase in temperature and it showed exponential type of nature. The results showed that the diffusion of hydrogen through the zeolite protective layer followed a Knudsen diffusion mechanism. The hydrogen permeation flux was slightly lower than a 1 pm thick Pd membrane, which may be attributed to the mass transfer resistance due to the zeolite protective layer on the outer surface of the membrane.

The stability of membrane M1 in the presence of lighter hydrocarbons (10%C ₃ H ₆ +10%C ₃ H ₈ ) was also evaluated at 600°C for 72 hours. Hydrogen permeation flux as a function of time in the stream is shown in Figure 7, which clearly depicts that the membrane performance is stable throughout the test period. In order to compare the results with the conventional unprotected Pd membrane, membrane M4, the hydrogen permeation was carried out in membrane M4 in the presence of propane and propylene at 600°C. The hydrogen permeation flux as a function of time in stream at different feed gas compositions is shown in Figure 8. The results indicate that the hydrogen flux of membrane M4 drastically decreased upon exposure to propylene. Membrane M4 supported on AI ₂ O ₃ showed quick deactivation upon exposed to C3H6, and the deactivation was due to the strong interaction of the hydrocarbon species on the membrane. When the membrane was exposed to the hydrocarbon at 600°C, the hydrocarbon cracking caused severe coke deposition on the membrane surface. The coke formation on the surface drastically decreased the hydrogen flux. Further increase in time of exposure spoiled the membrane and the hydrogen selectivity decreased sharply.

Comparing Figures 7 and 8, it can be observed that the unprotected Pd-membrane M4 is not stable even for 30 minutes in the presence of C3H6 and C3H8, whereas the membrane protected with zeolite protective layer, i.e. membrane M1, shows stable performance for 72 hours in presence of those contaminants. The zeolite protective layer acts as a protection barrier for the Pd-based selective layer of the membrane and selectively allows hydrogen to pass through it.

Figure 9 shows the SEM images of spent membranes M1 (Figure 9(a)) and M4 (Figures 9(b)) after the permeation test, which clearly shows growth of filamentous carbon fibres (Figure 9(c)) on the surface of the membrane M4. Due to vigorous carbon formation, membrane M4 was cracked and spoiled.

The spent membrane was further characterized by TGA to investigate the coke deposition on the membrane surface. The TGA of membrane M4 and membrane M1 are given in Figures 10 (a) and (b), respectively. It is evident from the figure that after exposure to 10% C3H6 + 10% C3H8 for 72 hours, there was minimal coke deposition on Pd surface and no deformation or cracks was found on the membrane M1. The small amount of carbon deposited on the membrane M1 may be due to thermal cracking of C3H8 and C3H6. It can therefore be deduced from that there was negligible coke formation on the membrane surface of membrane M1 since it comprised a zeolite protective layer. The hydrogen separation performance of each of membranes M1, M2, M3 and M4 was measured as a function of temperature. The results obtained are shown in Figure 11. The results show that the hydrogen flux of the unprotected membrane M4 decreased as the temperature increased, but membranes M1, M2 and M3 which comprised the zeolite protective layer, showed improved performance in the presence of hydrocarbons. The hydrogen flux of the three triple layered membranes M1, M2 and M3 increased with temperature, and showed an exponential behaviour with temperature. The hydrogen flux through the membranes M1 and M2 are nearly the same, but the hydrogen flux for the membrane M3 is less than membranes M1 and M2. Comparative results

There are prior art membranes in which a zeolite layer is provided directed on the Pd- based selective layer as a protective layer. Therefore, for a better basis of comparison of the membranes of the present invention with the prior art zeolite protected membrane, a membrane M5 was formed in which a Pd-based selective layer was formed on the outer circumferential side of the hollow fiber substrate and TS-1 zeolite protective layer was coated directly on the Pd-based selective layer by secondary growth method. The SEM image of the membrane M5 is shown in Figure 12, which showed non-uniform growth of the zeolite protective layer on the Pd-based selective layer. The growing of zeolite layer over metallic Pd layer may often be non-uniform and may lack adherence property due to mismatched matrix of the metallic layer and the ceramic substrate.

The membrane M5 was tested for hydrogen separation in the presence of hydrocarbons and the result was compared to the membrane M3. The results are shown in Figure 13. It can be seen that the hydrogen permeation decreased in presence of the hydrocarbons for membrane M5, and this may be due to the non- uniform zeolite protection layer formed over the Pd selective layer that allowed propane/propylene to come in contact with the membrane. The adsorption of the hydrocarbon compounds on the membrane surface resulted in decreased hydrogen flux. Additionally, at temperatures above 500°C, diffusion of Ti from the zeolite layer into the Pd selective layer may have occurred and resulted in a poor hydrogen permeation. Thus, it can be seen that the membrane of the present invention has superior performance compared to zeolite protected membranes known in the art.

Example 2

Applicability of membrane in catalytic activity of propane dehydrogenation reaction The applicability of membrane M1 was evaluated for propane dehydrogenation was using a catalytic membrane reactor. 7.5%Cr/Al ₂ C> ₃ catalyst was used for propane dehydrogenation reaction at 600°C using fixed bed reactor (FBR) and catalytic membrane reactor (CMR).

The formation of catalyst was analyzed by XRD and transmission electron microscopy. It could be concluded from the XRD of the catalyst (not shown) that the diffraction pattern of the fresh catalyst showed excellent dispersion of CrO _x in the mesoporous structure. No significant peak corresponding to CrO _x was detected in the diffraction pattern. The XRD pattern further indicated the poor crystallinity of the sample. The TEM images of the fresh catalyst depicted the incorporation of CrO _x species inside the hexagonal mesoporous structure. The EDS mapping of the catalyst also confirmed the well dispersion of CrO _x in the catalyst. Thus, the catalyst had excellent metal support interaction, which is a requisite parameter for a stable and higher catalytic activity. The activity of the catalyst was evaluated and the results were compared as shown in Fig. 14. The activity in the CMR was found to be higher than the FBR, and around 15% increment in the activity was achieved after integrating in the membrane reactor. The performance of the catalyst was relatively stable in the membrane reactor. However, there was a slow decrease in the catalyst activity in both the cases, which may be ascribed to the coke deposition on the catalyst. The coke deposition was mainly due to thermal C-C bond cleavage rather than the selective C-H bond breaking (as can be seen in Equations 1 and 2). These reactions given in equation, describe the possible pathways for formation of other impurities such as CH4 and C2H6 along with C3H6. The formation of these products decreased the selectivity of propane and caused coke deposition on catalyst, thereby decreasing the activity with time. The coke formation in the spent catalyst was evaluated by TGA analysis (not shown) which showed negligible coke formation on the catalyst. C ₃ H ₈ CH ₄ +C2H4 (1)

C2H4 +H2<® C2H6 (2)

It can be seen that the instantaneous removal of hydrogen from propane dehydrogenation reaction using a H ₂ permeable membrane increased the conversion compared to conversion in a fixed bed reactor. Thus, it can be concluded that the zeolite protective layer in membrane M1 plays a vital role in protecting the Pd-based selective layer of the membrane from coke formation (due to reaction with the hydrocarbons). The membrane is stable enough at high temperature and in the presence of contaminating gases. Further, the membrane reactor is successfully applied for propane dehydrogenation reaction. All these results confirm that the membrane of the present invention is suitable for different dehydrogenation and hydrogenation reactions of several hydrocarbons.

Example 3

Applicability of membrane in a membrane reactor for coupling propane dehydrogenation and carbon dioxide (CO ₂ ) metha nation reactions

A tubular membrane comprising a zeolite protective layer and a Pd-based selective layer on either surface of a support layer was formed in the manner similar to that described in Example 1 with reference to membrane M1. In particular, the zeolite protective layer comprised LTA and the selective layer comprised palladium. The zeolite protective layer was formed on the outer side while the Pd selective layer was formed on the inner side of a 12 mm outer diameter and 8 mm inner diameter tubular alumina support.

The performance of the membrane was evaluated by measuring the hydrogen flux through the membrane in the presence of contaminating gases like C ₃ H ₈ and C ₃ H ₆ , and the results showed a stable performance for 50 hours (see Figure 15). This proves the robustness of the membrane for hydrogen separation from the gas mixture containing hydrocarbon impurities.

The hydrogen flux in a membrane reactor depends on the hydrogen concentration difference across the membrane. It is well known that when a reactive gas is used in the sweep gas side that can consume hydrogen, this enhances the performance of membrane by creating a higher concentration gradient. To evaluate the performance, a bi-functional membrane reactor was constructed by packing two different catalysts on either side of the membrane for conducting propane dehydrogenation (PDH) and CO2 methanation reactions. A schematic representation of coupling the two reactions in a single membrane reactor is shown in Figure 16.

Pt-Sn based catalyst was packed on the outer side for PDH reaction and 10% Ni- CeZrO _x catalyst was packed in the inner side of the tubular membrane for CO2 methanation reaction. Around 5 g Pt-Sn/A C catalyst was used for PDH reaction, whereas 3 g of 10% Ni-CeZrO _x catalyst was packed inside for CO2 methanation reaction. The performance of the dual functional membrane reactor is shown in Figure 17.

The results clearly depict that upon coupling the reaction in a membrane reactor the activity of PDH reaction was enhanced. The degree of enhancement was higher at lower temperatures compared to the high temperature. The results can be ascribed to the higher amount of hydrogen consumption at lower temperatures.

The exothermic nature of the CO2 methanation reaction favoured higher CO2 conversion and hydrogen consumption at low temperatures. This resulted in a higher hydrogen concentration gradient across the membrane at low temperatures than the high temperature. Similarly, the CO2 methanation reaction in the membrane reactor was also higher at high temperature. This was due to the removal of hotspots from the exothermic CO2 methanation reaction by coupling with endothermic PDH reaction.

Further, the CH ₄ selectivity in CO2 methanation reaction was also enhanced after coupling in a membrane reactor compared to fixed bed reactor (FBR). The increased selectivity was due to the hydrogen spill over on the membrane surface. Thus, it can be seen that the membrane of the present invention is suitable for use in reactors in which two reactions are coupled in a single membrane reactor.

Example 4

Applicability of membrane in a membrane reactor for methane decomposition for high pure hydrogen production A membrane was formed similar to membrane M1 as described in Example 1 for use in a reactor for methane decomposition.

Catalytic dehydrogenation/decomposition of methane (CDM) is very important for the production of hydrogen from cheaper and abundant sources like natural gas. The decomposition follows the following reaction:

CH ₄ ® C + 2H ₂ (DH at 298K= 37.4 kJ mol ¹ H ₂ )

In this example, the applicability of the membrane for hydrogen production from methane pyrolysis reaction is studied. The outer zeolite protective layer was functionalized by active metals by forming phyllosilicate structure upon urea hydrolysis treatment. The modified layer acts as active catalytic centres for CH ₄ pyrolysis reaction as shown in Figure 18.

The zeolite protective layer was coated on the outer surface of the alumina substrate and Pd-based selective layer was formed on the inner surface. Additionally, an active Ni-silicate layer was grown on the surface of the zeolite protective layer for CH ₄ pyrolysis reaction. The modified zeolite protective layer acted as both catalyst for the CH ₄ pyrolysis reaction and as a protective layer for the Pd-based selective layer of the membrane. The catalytic membrane reactor provides benefits in multiple ways such as: a) catalyse the pyrolysis reaction, b) increase the hydrogen flux through the membrane by inhibiting the coke formation on the Pd-based selective layer and c) increase the yield of reaction, by selectively removing H ₂ .

For the catalytic methane decomposition reaction, a part of the zeolite protective layer was modified with a catalyst layer as shown in Figure 19.

The catalyst layer was grown on the membrane by urea hydrolysis method using Nickel nitrate hexa-hydrate (NiNC> ₃ )6H ₂ 0 solution. The Ni-precursor was dissolved in deionized water followed by addition of urea at a molar ratio of urea to Ni equals 8. Hydrothermal synthesis was conducted at 160°C for 8 hours using membrane M1 to grow the Ni-phyllosilicate over the zeolite protective layer. The Ni-phyllosilicate structure was formed due to the interaction of -Si-O- bond present in the zeolite matrix with Ni. The membrane prepared by this method was characterized by SEM analysis. The surface morphology of the membrane before and after modification is shown in Figure 20. The SEM image of the outer zeolite surface showed formation of sharper LTA zeolite (see Figure 20(b)). However, flower like layer structure was observed after the zeolite protective layer was modified by urea hydrolysis method indicating the formation of Ni- Phyllosilicate structure (see Figure 20(c)). The cross-sectional view of the outer layer confirmed the reduction of effective thickness of outer dense layer and formation of flower like layered structure on the top of a thin dense zeolite layer upon modification (Figure 20 (d)).

The performance of the membrane for hydrogen separation was evaluated and is shown in Figure 21. It was observed that the hydrogen flux of the membrane was higher than that of membrane M1. The difference in hydrogen flux was more prominent at lower temperatures compared to higher temperatures. The results can be ascribed to the catalytic nature of the Ni-particles on the zeolite layer for chemisorption of hydrogen. The presence of Ni-particles increased the hydrogen solubility of the zeolite layer, which contributed towards higher hydrogen flux of the Ni-PS modified zeolite layer. Further, the decreased effective thickness of the dense zeolite layer also decreased the diffusion resistance of gas molecules through the zeolite membrane. The hydrogen flux through the membrane was therefore enhanced after modification.

The catalytic membrane reactor was tested for CH4 pyrolysis reaction at 600°C and the results are shown in Figure 22. It is evident that the membrane showed excellent catalytic property, and around 62% of CH4 was converted to H2. However, the decomposition of CH4 resulted in deposition of coke on the active Ni-sites. Therefore, there was a sharp decrease in the initial activity and with progress of reaction the activity dropped down slowly. Moreover, high purity H2 (> 99.9% purity) was recovered from the reaction in the permeate side. The membrane was very effective in recovering the produced H2. However, due to the decrease in catalytic activity the partial pressure difference across the membrane decreased which, in turn decreased the hydrogen recovery in the permeated side with the progress of reaction.

Whilst the foregoing description has described exemplary embodiments, it will be understood by those skilled in the technology concerned that many variations may be made without departing from the present invention.