A bifunctional composite carrier and a preparation method and application thereof

Abstract

The application relates to the technical field of composite film materials, and particularly discloses a bifunctional composite carrier as well as a preparation method and application thereof. 1‑a X a The ceramic material is selected from at least one of Al2O3, ZrO2, YSZ, TiO2, SiC or MoSi2. The bifunctional composite carrier provided by the application has structural support strength and high-efficiency heating performance, effectively making up the blank in the prior art that no ideal support body material is used in the field of Joule heat and has excellent electric conductivity to realize rapid and uniform heating, a suitable pore structure to ensure low-resistance mass transfer, and excellent mechanical strength and stability at high temperatures.

Description

Technical Field

[0001] This invention relates to the field of separation membrane materials technology, and in particular to a bifunctional composite carrier, its preparation method, and its application. Background Technology

[0002] Membrane reactors, which couple separation and reaction processes, are a key technology for process intensification; however, their performance is highly dependent on operating temperature. Traditional external heating methods suffer from inherent drawbacks such as low heat transfer efficiency, slow response, large system size, and imprecise temperature control, limiting reactor efficiency and miniaturization. Joule heating technology, which achieves direct and efficient bulk heating through the material's own resistance, offers an ideal solution to these problems. Its millisecond-level high-speed response and near-100% energy conversion efficiency promise a revolutionary breakthrough in membrane reactor design.

[0003] However, successfully applying Joule heating technology to membrane reactors faces a serious core technical challenge: how to design and prepare an ideal support material that combines excellent electrical conductivity to achieve rapid and uniform heating, suitable pore structure to ensure low-resistance mass transfer, and excellent mechanical strength and stability at high temperatures.

[0004] Existing conventional material systems struggle to meet these multiple requirements: while single metallic conductors offer good conductivity, they are difficult to form stable porous structures and are prone to sintering at high temperatures; traditional ceramic insulators possess excellent porous structures and chemical stability, but lack conductive and heating capabilities; and the conventional strategy of simply physically mixing conductive materials (such as metal particles or carbon materials) with ceramic supports generally suffers from uneven phase distribution and poor interfacial stability. Under repeated thermal shocks during Joule heating, this can easily lead to conductive network failure, microstructural damage, or interfacial delamination, making it impossible to achieve stable and reliable self-heating functionality. This fundamental constraint at the material level has kept the development of Joule hot film reactors stagnant at the proof-of-concept stage for a long time.

[0005] Therefore, developing a Joule hot film reactor that can simultaneously combine excellent conductive pathways (to achieve efficient and uniform Joule heating effect), ideal porous channels (to ensure efficient transport of reactants and products), and outstanding mechanical strength and thermal stability is of great research significance in the field of advanced membrane technology. Summary of the Invention

[0006] In view of this, the present invention provides a bifunctional composite carrier, its preparation method, and its application. The high-entropy alloy / ceramic composite carrier overcomes the contradiction between conductivity and porous structure in existing Joule heating systems, enabling the high-entropy alloy / ceramic composite carrier to possess excellent electrical conductivity for rapid and uniform Joule heating, while also exhibiting an adjustable three-dimensional porous structure and high-temperature mechanical stability.

[0007] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0008] The first aspect of this invention provides a high-entropy alloy / metal oxide composite support with dual support and heating functions, wherein the high-entropy alloy comprises NiFeCrCoM 1-a X a Wherein, M is selected from any one or two of Cu, Al, Zn, Zr or Ti; X is selected from any one of Mo, W, V or Nb; 0.1≤a≤0.3; the ceramic material is selected from at least one of Al2O3, ZrO2, YSZ, TiO2, SiC or MoSi2.

[0009] Compared to existing technologies, this invention provides a bifunctional composite carrier with an interpenetrating structure of a high-entropy alloy and a ceramic material carrier. This composite carrier not only possesses excellent electrical conductivity but also features a composite structure of finger-like pores and sponge-like pores, along with a high specific surface area, ensuring efficient transport of reactants or products. Furthermore, the high-entropy alloy / ceramic material composite carrier of this invention exhibits excellent high-temperature mechanical strength and thermal shock stability. The high-entropy alloy, with its high hardness, high strength, and low density, enhances the carrier's resistance to compression and deformation when used together with the ceramic material as the carrier's framework. Due to the solid solution strengthening effect and passivation film characteristics of the high-entropy alloy (due to the formation of a dense oxide film by Cr), it maintains structural integrity even in high-temperature, humid, or corrosive environments, extending the composite carrier's service life. The increased thermal conductivity of the high-entropy alloy improves the thermal diffusivity of the composite carrier, enabling rapid and uniform heating. Moreover, the high-entropy alloy used in this invention has excellent electrical conductivity, allowing for Joule heating through electrical current.

[0010] Ceramic materials possess high hardness and compressive strength, serving as a rigid framework for composite carriers. They suppress plastic deformation of the high-entropy alloy matrix through "dispersion strengthening" or "particle reinforcement" effects. Furthermore, the high melting point of ceramic materials inhibits creep behavior in the composite carrier at high temperatures, ensuring dimensional stability during long-term high-temperature heating. More importantly, ceramic materials can form a synergistic conductive network with high-entropy alloys, improving Joule heating efficiency.

[0011] The dual-functional composite carrier provided by this invention combines structural support strength and efficient heating performance through material synergy. The technical solution of this invention effectively fills the gap in the prior art for an ideal support material that combines excellent electrical conductivity to achieve rapid and uniform heating, suitable pore structure to ensure low-resistance mass transfer, and excellent mechanical strength and stability at high temperatures in the field of Joule heating.

[0012] Preferably, the molar ratio of each element in the high-entropy alloy is 1:1:1:1:1-a:a, where 0.1≤a≤0.3.

[0013] Preferably, the high-entropy alloy is NiFeCrCoCu. 0.8 Mo 0.2 NiFeCrCoAl 0.8 V 0.2 or NiFeCrCoZn 0.8 Nb 0.2 At least one of them.

[0014] More preferably, the high-entropy alloy NiFeCrCoCu 0.8 Mo 0.2 NiFeCrCoAl 0.8 V 0.2 or NiFeCrCoZn 0.8 Nb 0.2 The molar ratio of each element in the mixture is 1:1:1:1:0.8:0.2.

[0015] Preferably, the mass ratio of the high-entropy alloy to the ceramic material in the high-entropy alloy / ceramic material composite carrier is 1-5:5-9.

[0016] More preferably, the mass ratio of the high-entropy alloy to the ceramic material in the high-entropy alloy / ceramic material composite carrier is 2-4:6-9.

[0017] A second aspect of the present invention provides a method for preparing the bifunctional composite carrier, comprising the following steps:

[0018] Step 1: Weigh the ceramic material powder, high-entropy alloy metal powder, pore-forming agent, organic polymer, additives and organic solvent according to the design ratio, mix them evenly, and ball mill them to obtain a suspension slurry;

[0019] Step 2: The suspension slurry is extruded through a spinning nozzle using a high-pressure injection pump and formed in an ice-water bath to obtain a hollow fiber precursor.

[0020] Step 3: Dry the hollow fibrous precursor, heat it to 1200-1500℃ in a micro-reducing atmosphere for sintering, and cool it to obtain the bifunctional composite carrier.

[0021] Preferably, in step one, the pore-forming agent is graphite, starch, or polymethyl methacrylate (PMMA) microspheres.

[0022] Preferably, in step one, the amount of pore-forming agent added is 5%-30% of the total mass of the ceramic material powder and the high-entropy alloy metal precursor.

[0023] Preferably, in step one, the organic polymer is any one or more of polysulfone, polyethersulfone, polyacrylonitrile, or polyetherimide.

[0024] Preferably, in step one, the amount of the organic polymer added is 60%-80% of the total mass of the ceramic material powder and the high-entropy alloy metal precursor.

[0025] Preferably, in step one, the additives include thickeners and dispersants.

[0026] Preferably, in step one, the total amount of the additive is 1%-5% of the total mass of the ceramic material powder and the high-entropy alloy metal precursor; wherein the additive includes a thickener and a dispersant in a mass ratio of 1:1-1:1.5.

[0027] More preferably, the thickener is polyvinyl alcohol or polyvinylpyrrolidone.

[0028] More preferably, the dispersant is polyacrylamide.

[0029] Preferably, in step one, the organic solvent is one or more of N-methylpyrrolidone, N,N-dimethylamide, N,N-dimethylacetamide, or dimethyl sulfoxide.

[0030] Preferably, in step one, the volume-to-mass ratio of the amount of organic solvent added to the total mass of the ceramic material powder and the high-entropy alloy metal precursor is 0.2 mL:1 g to 0.5 mL:1 g.

[0031] Preferably, in step one, the ball milling speed is 500-700 rpm and the ball milling time is 2-3 hours.

[0032] Preferably, in step two, the diameter of the spinning nozzle is 2-3 mm, and the extrusion rate is 1-5 mL / min.

[0033] Preferably, in step two, the micro-reducing atmosphere is a mixture of hydrogen and argon, wherein the volume percentage of hydrogen is 5%-10% of the volume of the mixture.

[0034] Preferably, in step three, the sintering treatment time is 5-12 hours.

[0035] Preferably, in step three, the temperature is raised to 1200-1500℃ using a programmed temperature rise method, with a heating rate of 2-5℃ / min.

[0036] A third aspect of the present invention provides a composite membrane reactor, including the aforementioned bifunctional composite carrier.

[0037] The fourth aspect of this invention provides a method for preparing the composite membrane reactor, specifically comprising the following steps:

[0038] S1. Polish and clean the dual-functional composite carrier to obtain a pretreated composite carrier;

[0039] S2. A functional separation layer is grown on the surface of the pretreated composite carrier, washed, dried, and calcined at 300-500℃ to obtain a composite membrane reactor.

[0040] Preferably, in S2, the method of growing the functional separation layer includes any one or more of chemical vapor deposition, sol-gel method, or hydrothermal synthesis method.

[0041] Preferably, in S2, the functional separation layer is any one of a microporous zeolite membrane, a metal-organic framework membrane, or a dense palladium alloy membrane.

[0042] Preferably, in S2, the calcination time is 2-6 hours.

[0043] The fifth aspect of this invention provides the application of the composite membrane reactor in the field of catalytic reforming for hydrogen production.

[0044] In summary, this invention provides a bifunctional composite carrier, its preparation method, and its applications. The high-entropy alloy / ceramic composite carrier possesses excellent mechanical strength, high electrical conductivity, and self-heating Joule heating capability. Upon energization, it can rapidly heat to 800-1000℃ with uniform temperature distribution, completely eliminating the need for external heating devices. Furthermore, the composite carrier provided by this invention exhibits excellent high-temperature creep resistance, thermal shock stability, and rapid Joule heating response. Due to the presence of the high-entropy alloy, carbon deposition and sulfidation are effectively suppressed, resulting in a longer service life for membrane reactors prepared using it. In addition, the bifunctional composite carrier provided by this invention has low raw material costs, strong process compatibility, and extremely high industrialization value and broad application prospects. Attached Figure Description

[0045] Figure 1 The NiFeCrCoCu with dual support and heating functions provided in Example 1 0.8 Mo 0.2 Cross-sectional scanning electron microscope image of the Al2O3 composite support;

[0046] Figure 2 The NiFeCrCoCu with dual support and heating functions provided in Example 1 0.8 Mo 0.2 Magnified scanning electron microscope image of the cross-section of the Al2O3 composite support;

[0047] Figure 3The NiFeCrCoCu with dual support and heating functions provided in Example 1 0.8 Mo 0.2 Scanning electron microscope image of the outer surface of the Al2O3 composite support. Detailed Implementation

[0048] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0049] Example 1

[0050] This embodiment provides a NiFeCrCoCu with dual functions of support and heating. 0.8 Mo 0.2 The Al2O3 composite support and its preparation method are detailed below:

[0051] NiFeCrCoCu 0.8 Mo 0.2 / Al2O3 composite support NiFeCrCoCu 0.8 Mo 0.2 The mass ratio of NiFeCrCoCu to Al2O3 is 3:7; wherein, NiFeCrCoCu 0.8 Mo 0.2 The molar ratio of each element in the mixture is 1:1:1:1:0.8:0.2.

[0052] The NiFeCrCoCu with dual support and heating functions 0.8 Mo 0.2 The preparation method of the Al2O3 composite support includes the following steps:

[0053] Step 1: Weigh 70g Al2O3 powder, 5.96g nickel, 5.67g iron powder, 5.28g chromium, 5.98g cobalt, 5.16g copper, 1.95g molybdenum, 25g graphite, 80g polysulfone, 2g polyvinyl alcohol, 2g polyacrylamide, and 40mL N-methylpyrrolidone according to the designed ratio, mix them evenly, and ball mill them at 600rpm for 2.5h to obtain a suspension slurry.

[0054] Step 2: The suspension slurry is extruded through a spinning nozzle with a diameter of 2 mm using a high-pressure injection pump at an extrusion rate of 3 mL / min. The mixture is then molded in an ice-water bath to obtain a hollow fibrous precursor with an outer diameter of 2 mm and an inner diameter of 1 mm.

[0055] Step 3: Dry the hollow fibrous precursor and sinter it at 1300℃ for 6 hours under a micro-reducing atmosphere (a mixture of hydrogen and argon, where the volume of hydrogen accounts for 10% of the mixed atmosphere volume) at a heating rate of 5℃ / min. After cooling, the NiFeCrCoCu with dual supporting and heating functions is obtained. 0.8 Mo 0.2 / Al2O3 composite support.

[0056] Example 2

[0057] This embodiment provides a NiFeCrCoAl with dual support and heating functions. 0.8 V 0.2 The ZrO2 composite support and its preparation method are detailed below:

[0058] NiFeCrCoAl 0.8 V 0.2 NiFeCrCoAl in ZrO2 composite support 0.8 V 0.2 The mass ratio of NiFeCrCoAl to ZrO2 is 2:8; wherein, the NiFeCrCoAl 0.8 V 0.2 The molar ratio of each element in the mixture is 1:1:1:1:0.8:0.2.

[0059] The NiFeCrCoAl with dual support and heating functions 0.8 V 0.2 The preparation method of the / ZrO2 composite support includes the following steps:

[0060] Step 1: Weigh 80g ZrO2 powder, 4.56g nickel, 4.33g iron powder, 4.04g chromium, 4.58g cobalt, 1.68g aluminum, 0.79g vanadium, 25g graphite, 80g polysulfone, 2g polyvinyl alcohol, 2g polyacrylamide, and 45mL N-methylpyrrolidone according to the designed ratio, mix them evenly, and ball mill them at 650rpm for 2.5h to obtain a suspension slurry.

[0061] Step 2: The suspension slurry is extruded through a spinning nozzle with a diameter of 2 mm using a high-pressure injection pump at an extrusion rate of 3 mL / min. The mixture is then molded in an ice-water bath to obtain a hollow fibrous precursor with an outer diameter of 2 mm and an inner diameter of 1 mm.

[0062] Step 3: Dry the hollow fibrous precursor and sinter it at 1280℃ for 8 hours in a micro-reducing atmosphere (a mixture of hydrogen and argon, where the volume of hydrogen accounts for 10% of the mixed atmosphere volume) at a heating rate of 5℃ / min. After cooling, obtain the NiFeCrCoAl with dual supporting and heating functions.0.8 V 0.2 / ZrO2 composite carrier.

[0063] Example 3

[0064] This embodiment provides a NiFeCrCoZn with dual support and heating functions. 0.8 Nb 0.2 The TiO2 composite support and its preparation method are detailed below:

[0065] NiFeCrCoZn 0.8 Nb 0.2 / TiO2 composite support NiFeCrCoZn 0.8 Nb 0.2 The mass ratio of NiFeCrCoZn to Al2O3 is 2.9:7.1; wherein, NiFeCrCoZn 0.8 Nb 0.2 The molar ratio of each element in the mixture is 1:1:1:1:0.8:0.2.

[0066] The NiFeCrCoZn with dual support and heating functions 0.8 Nb 0.2 The preparation method of the / TiO2 composite support includes the following steps:

[0067] Step 1: Weigh 71g TiO2 powder, 5.73g nickel, 5.45g iron powder, 5.09g chromium, 5.75g cobalt, 5.12g zinc, 1.87g niobium, 25g graphite, 80g polysulfone, 2g polyvinyl alcohol, 2g polyacrylamide and 35mL N-methylpyrrolidone according to the designed ratio, mix them evenly, and ball mill at 700rpm for 2h to obtain a suspension slurry;

[0068] Step 2: The suspension slurry is extruded through a spinning nozzle with a diameter of 2 mm using a high-pressure injection pump at an extrusion rate of 5 mL / min. The mixture is then molded in an ice-water bath to obtain a hollow fibrous precursor with an outer diameter of 2 mm and an inner diameter of 1 mm.

[0069] Step 3: Dry the hollow fibrous precursor and sinter it at 1350℃ for 6 hours under a micro-reducing atmosphere (a mixture of hydrogen and argon, where the volume of hydrogen accounts for 10% of the mixed atmosphere volume) at a heating rate of 5℃ / min. After cooling, the NiFeCrCoZn with dual supporting and heating functions is obtained. 0.8 Nb 0.2 / TiO2 composite support.

[0070] Comparative Example 1

[0071] This comparative example provides a nickel-based alloy NiNb65 The Al2O3 composite support and its preparation method are detailed below:

[0072] The NiNb 65 The preparation method of the Al2O3 composite support includes the following steps:

[0073] Step 1: Weigh 70g Al2O3 powder, 10.5g nickel, 19.5g niobium, 25g graphite, 80g polysulfone, 2g polyvinyl alcohol, 2g polyacrylamide and 40mL N-methylpyrrolidone according to the design ratio, mix them evenly, and ball mill them at 600rpm for 2.5h to obtain a suspension slurry.

[0074] Step 2: The suspension slurry is extruded through a spinning nozzle with a diameter of 2 mm using a high-pressure injection pump at an extrusion rate of 3 mL / min, and then formed in an ice-water bath to obtain a hollow fiber precursor.

[0075] Step 3: Dry the hollow fibrous precursor and sinter it at 1300℃ for 6 hours in a micro-reducing atmosphere (a mixture of hydrogen and argon, where the volume of hydrogen accounts for 10% of the mixed atmosphere volume) at a heating rate of 5℃ / min. After cooling, obtain the NiNb. 65 / Al2O3 composite support.

[0076] To further demonstrate the technical effects of the present invention, a separation membrane was deposited on the surface of the composite carriers obtained in Examples 1-3 and Comparative Example 1 to prepare a composite membrane reactor, as specifically described in the experimental examples.

[0077] Test case

[0078] S1. The composite carrier is cleaned to obtain a pretreated composite carrier;

[0079] S2. Palladium hexafluoroacetylacetone (Pd(hfac)2) and copper hexafluoroacetylacetone (Cu(hfac)2) vapors were flowed through the inside of the support at 550°C for 2 hours at a molar ratio of 1:3 to make the Pd-Cu film about 2 μm thick. Then, it was annealed in hydrogen at 400°C for 1 hour to form a dense Pd-Cu alloy film layer, thus obtaining a composite membrane reactor.

[0080] Application performance testing: The composite membrane reactor was energized and the time it took to reach 800°C was tested. The composite membrane reactor was also used to test hydrogen recovery. The composite membrane reactor was fixed in a custom hollow fiber permeation tank. The shell side of the membrane was the feed zone, and the lumen side was the permeation zone. The feed zone was connected to an H2 / He mixed gas supply pipeline, the permeation zone was connected to an N2 purge gas pipeline and a gas chromatograph inlet, and the retention zone (feed zone outlet) was also connected to a gas chromatograph inlet, forming a three-terminal detection pathway of "feed-permeation-retention".

[0081] Test parameter settings: Temperature range: 400-1000℃, set test temperature points at 100℃ intervals, and hold each temperature point for 30 minutes until the system stabilizes.

[0082] Gas parameters: H2 / He mixed gas (H2 concentrations of 10 vol.%, 50 vol.%, and 90 vol.%) is introduced into the feed side at a total flow rate of 30 mL / min; N2 purge gas is introduced into the permeate side at a flow rate of 60 mL / min; the system pressure is maintained at atmospheric pressure (0.1 MPa) to avoid damage to the membrane structure caused by high pressure.

[0083] Data acquisition and calculation: After the system stabilizes at each temperature point, the gas composition on the permeation side and the retention side is detected by gas chromatography, and the volume fractions of H2 and N2 are recorded. At the same time, the total gas flow rate on the permeation side and the retention side is measured by soap bubble flow meter.

[0084] The hydrogen permeation flux, H2 / N2 selectivity, and stable operating time were tested, and the test results are shown in Table 1.

[0085] Table 1 Application Performance Test Results

[0086]

[0087] The present invention also relates to the NiFeCrCoCu with dual support and heating functions obtained in Example 1. 0.8 Mo 0.2 The Al2O3 composite support was subjected to scanning electron microscopy (SEM) analysis, and the results are as follows: Figure 1-3 As shown, where, Figure 1 The complete macroscopic morphology of the composite carrier is shown, exhibiting a hollow fiber morphology with regular structure and uniform texture, providing an ideal matrix for the subsequent deposition of the functional separation layer.

[0088] Figure 2 The image reveals the interpenetrating structure of the composite support, and at this high magnification, high-entropy alloy phases (such as NiFeCrCoCu) can be clearly observed. 0.8 Mo 0.2 The relationship between the phase and the ceramic phase (such as Al2O3) is not a simple physical mixture or layering, but rather forms a continuous, uniform, interwoven, and permeable three-dimensional network. The interfaces between the two phases are tightly bonded, with no obvious gaps or phase separation. This unique interpenetrating structure provides the composite carrier with a continuous electronic conduction path, a robust mechanical framework, and ideal porous channels.

[0089] Figure 3 The outer surface of the composite carrier is shown, further confirming the formation and uniformity of the interpenetrating structure. Figure 3The surface of the carrier is shown to be composed of high-entropy alloy and ceramic particles, with uniform distribution and dense bonding between the two phases. This uniform surface structure is a natural extension of the internal three-dimensional interpenetrating network, providing an ideal substrate with suitable roughness and uniform chemical properties for subsequent growth of functional separation layers (such as dense Pd-Cu alloy films) by methods such as chemical vapor deposition, ensuring the integrity and high selectivity of the separation layer.

[0090] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions or improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A dual-functional composite carrier, characterized in that: The bifunctional composite carrier is an interpenetrating structure of a high-entropy alloy and a ceramic material carrier; wherein, the high-entropy alloy is NiFeCrCoM 1-a X a M is selected from any one or two of Cu, Al, Zn, Zr or Ti; X is selected from any one of Mo, W, V or Nb; 0.1≤a≤0.3; the ceramic material is selected from at least one of Al2O3, ZrO2, YSZ, TiO2, SiC or MoSi2.

2. The dual-functional composite carrier as described in claim 1, characterized in that: The high-entropy alloy is NiFeCrCoCu 0.8 Mo 0.2 NiFeCrCoAl 0.8 V 0.2 or NiFeCrCoZn 0.8 Nb 0.2 At least one of them.

3. The dual-functional composite carrier as described in claim 1 or 2, characterized in that: The mass ratio of high-entropy alloy to ceramic material in the bifunctional composite carrier is 1-5:5-9.

4. The method for preparing the bifunctional composite carrier according to any one of claims 1-3, characterized in that: Includes the following steps: Step 1: Weigh the ceramic material powder, high-entropy alloy metal precursor, pore-forming agent, organic polymer, additives and organic solvent according to the design ratio, mix them evenly, and ball mill them to obtain a suspension slurry. Step 2: The suspended slurry is extruded through a spinning nozzle using a high-pressure injection pump to form a hollow fiber precursor. Step 3: Dry the hollow fibrous precursor, heat it to 1200-1500℃ in a micro-reducing atmosphere for sintering, and then cool it to obtain a bifunctional composite carrier.

5. The method for preparing the bifunctional composite carrier as described in claim 4, characterized in that: In step one, the amount of pore-forming agent added is 5%-30% of the total mass of ceramic material powder and high-entropy alloy metal precursor; the pore-forming agent is graphite, starch or polymethyl methacrylate microspheres; In step one, the amount of the organic polymer added is 60%-80% of the total mass of the ceramic material powder and the high-entropy alloy metal precursor; the organic polymer is any one or more of polysulfone, polyethersulfone, polyacrylonitrile, or polyetherimide. In step one, the total amount of the additive is 1%-5% of the total mass of the ceramic material powder and the high-entropy alloy metal precursor; wherein, the additive includes a thickener and a dispersant in a mass ratio of 1:1-1:1.

5. In step one, the volume-to-mass ratio of the amount of organic solvent added to the total mass of the ceramic material powder and the high-entropy alloy metal precursor is 0.2 mL:1 g to 0.5 mL:1 g; the organic solvent is one or more of N-methylpyrrolidone, N,N-dimethylamide, N,N-dimethylacetamide or dimethyl sulfoxide.

6. The method for preparing the bifunctional composite carrier as described in claim 5, characterized in that: In step one, the ball mill rotates at 500-700 rpm and the milling time is 2-3 hours. In step one, the thickener is polyvinyl alcohol or polyvinylpyrrolidone; In step one, the dispersant is polyacrylamide; In step two, the extrusion rate is 1-5 mL / min; In step two, the micro-reducing atmosphere is a mixture of hydrogen and argon, wherein the volume percentage of hydrogen is 5%-10%. In step two, the sintering process takes 5-12 hours. In step two, the temperature is raised to 1200-1500℃ using a programmed temperature rise method, with a heating rate of 2-5℃ / min.

7. A composite membrane reactor, characterized in that: Includes the bifunctional composite carrier as described in any one of claims 1-3.

8. The method for preparing the composite membrane reactor as described in claim 7, characterized in that: Specifically, the steps include the following: S1. Polish and clean the bifunctional composite carrier to obtain a pretreated composite carrier; S2. A functional separation layer is grown on the surface of the pretreated composite carrier, washed, dried, and calcined at 300-500℃ to obtain a composite membrane reactor.

9. The method for preparing the composite membrane reactor as described in claim 8, characterized in that: In S2, the method of growing the functional separation layer includes any one or more of chemical vapor deposition, sol-gel method or hydrothermal synthesis method; In S2, the functional separation layer is any one of a microporous zeolite membrane, a metal-organic framework membrane, or a dense palladium alloy membrane; In S2, the calcination time is 2-6 hours.

10. The application of the composite membrane reactor as described in claim 7 in the field of catalytic reforming for hydrogen production.

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