Novel CO2-resistant high-flux biphase oxygen-permeable membrane material and preparation method thereof

Abstract

The invention discloses a CO2-resistant high-flux novel dual-phase oxygen-permeable membrane material and a preparation method thereof, and a perovskite phase of the CO2-resistant high-flux novel dual-phase oxygen-permeable membrane material is double-doped at B sites of Cu < 2 + > and Nb < 5 + > on the basis of SrFeO3-delta-based ABO3 type perovskite oxide with mixed ion electron conduction. The preparation method has the beneficial effect that the oxygen permeation rate of the double-phase oxygen permeation membrane is improved. From the perspective of the preparation method of the material, the mass ratio of two phases, the thickness of the membrane and the like, the balance between the stability and the oxygen permeation rate is realized by combining the influence of a sintering schedule on the mechanical properties of the biphase oxygen permeation membrane.

Description

Technical Field

[0001] The present invention belongs to the technical field of mixed conductor oxygen permeable membranes, and particularly relates to a novel high-flux dual-phase oxygen permeable membrane material resistant to CO2 and a preparation method thereof. Background Art

[0002] Under the background of the "dual carbon goal", the demand for pure oxygen in the energy field is increasing day by day. As an inorganic dense ceramic membrane with both oxygen ion and electron mixed conduction properties, the mixed conductor oxygen permeable membrane can selectively separate pure oxygen from the air and has attracted much attention. However, the trade-off between the stability of the oxygen permeable membrane and the oxygen permeation flux has always been a bottleneck problem restricting its industrial application. The IC-MIEC type dual-phase oxygen permeable membrane composed of fluorite materials with oxygen ion conduction (IC) and perovskite materials with mixed ion electron conduction (MIEC) shows superior stability compared to single-phase perovskite oxygen permeable membranes and has become a research hotspot in recent years. However, at present, it is still impossible to meet the industrial requirements of high-flux stable operation in harsh atmospheres such as CO2 (1 mL·min -1 ·cm -2 ). Therefore, developing a novel oxygen permeable membrane with both high oxygen permeability and stability, and systematically exploring the influence rules and action mechanisms of various factors on the oxygen permeation performance during the oxygen separation process is of great significance for promoting the industrial application of oxygen permeable membranes. Summary of the Invention

[0003] In view of this, the present invention aims to provide a novel high-flux dual-phase oxygen permeable membrane material resistant to CO2 and a preparation method thereof to solve at least one technical problem in the background art.

[0004] To achieve the above object, the technical solution of the present invention is realized as follows: A novel high-flux dual-phase oxygen permeable membrane material resistant to CO2, the novel high-flux dual-phase oxygen permeable membrane material resistant to CO2 is 58.47wt% SDC(Co)-41.53wt% Sm 0.4 Sr 0.6 Cu 0.2 Fe 0.7 Nb 0.1 O 3-δ .

[0005] Furthermore, the perovskite phase of the novel high-flux dual-phase oxygen permeable membrane material resistant to CO2 is based on the SrFeO with mixed ion electron conduction 3-δ -type ABO3-type perovskite oxide, and is double-doped at the B-site with Cu 2+ and Nb 5+ .

[0006] Furthermore, the fluorite phase of the novel high-flux dual-phase oxygen permeable membrane material resistant to CO2 is in Ce0.8 Sm 0.2 O 2-δ On this basis, 1.5 - 2.5 mol% of Co element is added in the way of grain boundary preferential segregation.

[0007] Furthermore, the mass ratio of the fluorite phase to the perovskite phase of the high - flux novel dual - phase oxygen - permeable membrane material resistant to CO₂ is 55 - 60:40 - 45.

[0008] Furthermore, the Sr content at the A site in the perovskite phase of the high - flux novel dual - phase oxygen - permeable membrane material resistant to CO₂ is 0.6.

[0009] The preparation method of the above - mentioned high - flux novel dual - phase oxygen - permeable membrane material resistant to CO₂ includes the following steps: S1: Weigh the metal nitrates contained in the perovskite phase and the metal nitrates contained in the fluorite phase respectively and place them in deionized water. Heat and stir them respectively. After complete dissolution, add complexing agents to obtain metal ion solutions. Roast the preliminary fluorite - phase powder and the preliminary perovskite - phase powder, add the sintering aid element Co in the way of grain boundary preferential segregation, and finally grind them respectively to obtain the perovskite - phase powder and the fluorite - phase powder; S2: Granulate and dry - press the perovskite - phase powder and the fluorite - phase powder prepared in step S1, and then sinter them densely in a high - temperature muffle furnace.

[0010] Furthermore, the metal nitrates contained in the perovskite phase in step S1 include cerium salt, samarium salt, iron salt, strontium salt, niobium salt, and copper salt; The metal nitrates contained in the fluorite phase in step S1 include cerium salt, samarium salt, iron salt, strontium salt, niobium salt, and copper salt; The heating and stirring in step S1 include stirring at 70 - 90 °C until complete dissolution, and adding H₂O₂ during stirring; The complexing agent in step S1 includes EDTA acid and citric acid, and the pH of the solution is adjusted with ammonia water to obtain the metal ion solution; Adding the sintering aid element Co in the way of grain boundary preferential segregation in step S1 includes weighing the corresponding content of cobalt nitrate hexahydrate (Co(NO₃)₂·6H₂O), putting it into an ethanol solution, grinding, then soaking the prepared initial powder in the cobalt nitrate solution, and drying the obtained mixture by stirring and grinding in an agate mortar to obtain the final powder.

[0011] Furthermore, the cerium salt includes cerium nitrate hexahydrate; The samarium salt includes samarium nitrate hexahydrate; The copper salt includes copper nitrate; The iron salt includes iron nitrate nonahydrate; The strontium salt includes strontium nitrate; The niobium salt includes ammonium oxalate niobate.

[0012] Furthermore, in step S2, a two-step sintering technique is used in a high-temperature muffle furnace to achieve a dense sintering process. After the temperature is raised to 1080-1120°C, the temperature is maintained for 8-12 minutes, and then the temperature is increased to 8-12°C·min -1 The temperature is rapidly reduced to 1000-1050℃, and then kept warm for a long time in the remaining time, with a total holding time of 4-6h, and then heated at 1-3℃·min -1 The temperature was reduced to 190-210°C at a rate of 1.

[0013] The perovskite phase of the material is SrFeO with mixed ion-electron conduction 3-δ Based on ABO3 type perovskite oxide, through low-valent Cu 2+ With fixed high valence Nb 5+ The double doping at the B position of the fluorite phase achieves the stability of the dual-phase oxygen permeable membrane in harsh atmospheres such as CO2. 0.8 Sm 0.2 O 2-δ On the basis of SDC, 2 mol% Co element is added in the form of grain boundary preferential segregation to improve its electrical conductivity and electronic conductivity. By weakening the oxygen ion conduction limitation in the two-phase membrane, extending the three-phase boundary (TPB) where the oxygen surface exchange reaction (OSER) occurs to the entire membrane surface, it can reduce the blocking effect of electronic conduction in the fluorite phase and improve the oxygen permeability of the two-phase oxygen permeable membrane. From the perspective of material modification such as material preparation method, two-phase mass ratio, membrane thickness, and the influence of sintering system on the mechanical properties of the two-phase oxygen permeable membrane, a new type of high-flux two-phase oxygen permeable membrane 58.47wt%SDC(Co)-41.53wt%Sm was finally prepared to resist CO2. 0.4 Sr 0.6 Cu 0.2 Fe 0.7 Nb 0.1 O 3-δ (58.47wt%SDC(Co)-41.53wt%SSCFN6).

[0014] Compared with the prior art, the novel high-flux dual-phase oxygen permeable membrane material resistant to CO2 and the preparation method thereof described in the present invention have the following advantages: The present invention conducts modification research on the perovskite phase and solves the problem of working stability of the dual-phase oxygen permeable membrane in harsh atmospheres such as CO2. Based on the SDC, the fluorite phase is added with a 2 mol% content of Co element in the form of preferential grain boundary segregation to improve the oxygen permeability of the dual-phase oxygen permeable membrane. From the perspectives of material preparation method, two-phase mass ratio, membrane thickness, etc., and combined with the influence of sintering system on the mechanical properties of the dual-phase oxygen permeable membrane, a balance between stability and oxygen permeability is achieved, and finally a new high-flux dual-phase oxygen permeable membrane resistant to CO2 is prepared, enriching the design concept of oxygen permeable membrane. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] The accompanying drawings, which form a part of the present invention, are used to provide a further understanding of the present invention. The schematic embodiments and descriptions thereof of the present invention are used to explain the present invention and do not constitute an improper limitation to the present invention. In the drawings: Figure 1 XRD patterns of biphasic oxygen permeable membrane samples with different Sr contents in the embodiments of the present invention; Figure 2 (a) Morphology of sintered dense 2Co-SDC-SSCFN4; (b) Morphology of 2Co-SDC-SSCFN5; (c) Morphology of 2Co-SDC-SSCFN6; (d) Elemental EDS distribution corresponding to 2Co-SDC-SSCFN6 in the embodiments of the present invention; Figure 3 Biphasic membranes of 2Co-SDC-SSCFN6 prepared by different powder synthesis methods in the embodiments of the present invention, (a) Oxygen permeation rate as a function of temperature in an air / He gradient and (b) Corresponding Arrhenius relationship; Figure 4 Biphasic membranes of x wt% SDC(Co)-(100-x)wt% SSCFN6 (x = 30, 40, 50, 60 and 70) in the embodiments of the present invention, Relationship between oxygen permeation rate and temperature (a) and corresponding Arrhenius curve (b); Figure 5 Fitting relationship of oxygen permeation rate of biphasic membranes with different mass ratios of two phases in the embodiments of the present invention; Figure 6 Relationship between oxygen permeation flux and reciprocal of thickness at different temperatures in the embodiments of the present invention; Figure 7 XRD patterns of the air side and purge side after long-term stability test of 58.47wt% SDC(Co)-41.53wt% SSCFN6 in the embodiments of the present invention; Figure 8 Schematic diagrams of (a) CS traditional sintering process and (b) TSS two sintering techniques in the embodiments of the present invention; Figure 9 Image of the sample indentation under a light microscope in the embodiments of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0016] It should be noted that, without conflict, the embodiments in the present invention and the features in the embodiments may be combined with each other.

[0017] The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0018] This application provides a high-throughput novel dual-phase oxygen permeable membrane material resistant to CO2. This material includes a perovskite phase in SrFeO with mixed ionic and electronic conduction 3-δ based ABO3-type perovskite oxide. Through double doping of the B site with low-valence Cu 2+ and fixed high-valence Nb 5+ the stability of the dual-phase oxygen permeable membrane in harsh atmospheres such as CO2 is achieved.

[0019] In the described material, the fluorite phase is based on Ce 0.8 Sm 0.2 O 2-δ (SDC). 2 mol% of Co element is added in the way of grain boundary preferred segregation.

[0020] In the described material, the mass ratio of the fluorite phase to the perovskite phase is 58.47:41.53.

[0021] For the novel dual-phase oxygen permeable membrane material, the content of Sr at the A site in the perovskite phase is 0.6.

[0022] A preparation method of a high-throughput novel dual-phase oxygen permeable membrane material resistant to CO2 includes the following steps: Firstly, powders are prepared by a one-pot sol-gel method. According to the chemical formula of the described material, the required cerium salts, samarium salts, iron salts, strontium salts, niobium salts, copper salts, etc. are calculated and accurately weighed, and added to an appropriate amount of water. After heating and stirring at 85 °C until completely dissolved, a metal ion solution is obtained. During the process, H2O2 is used to oxidize oxalate ions to ensure the dissolution of Nb 5+ Slowly add EDTA acid and citric acid, and adjust the pH of the solution with ammonia water. Continue heating and stirring until the solution becomes gel-like. After placing it in a drying oven and presenting a black and fluffy state, the sample is taken out and heated in a flat furnace to burn off organic substances. After stirring until there are no sparks, it is placed in a low-temperature muffle furnace for heat preservation to obtain preliminary powders. Weigh the corresponding content of cobalt salts and put them into an ethanol solution, grind to accelerate their dissolution, then soak the prepared initial powders in the cobalt nitrate solution. The obtained mixture is stirred, ground, and dried in an agate mortar to obtain the final powders.

[0023] (2) Weigh 0.5 mm thick prepared powders. After processes such as granulation and dry pressing, sinter them densely in a high-temperature muffle furnace using a two-step sintering technique. Raise the temperature to T1, keep it warm for t1, then quickly cool to T2 at a rate of 10 °C·min -1 and keep it warm for a long time during the remaining time, where the total heat preservation time is t2. Subsequently, cool it to 200 °C at a rate of 2 °C·min -1 to ensure that the membrane has the optimal mechanical properties.

[0024] (3) In step (1), the cerium salt is cerium nitrate hexahydrate (Ce(NO3)3·6H2O), the samarium salt is samarium nitrate hexahydrate (Sm(NO3)3·6H2O), the copper salt is copper nitrate (Cu(NO3)2), the cobalt salt is cobalt nitrate hexahydrate (Co(NO3)2·6H2O), the iron salt is iron nitrate nonahydrate (Fe(NO3)3·9H2O), the strontium salt is strontium nitrate Sr(NO3)2, and the niobium salt is ammonium niobium oxalate C4H4NNbO9.nH2O.

[0025] In step (2), T1 = 1100 °C, T2 = 1050 °C, t1 = 10 min, and t2 = 5 h.

[0026] A novel high-flux dual-phase oxygen permeable membrane material resistant to CO2 and its preparation method are as follows: Use the one-pot sol-gel method to prepare the powder. Calculate and accurately weigh the required cerium nitrate hexahydrate (Ce(NO3)3·6H2O), samarium nitrate hexahydrate (Sm(NO3)3·6H2O), copper nitrate (Cu(NO3)2), iron nitrate nonahydrate (Fe(NO3)3·9H2O), strontium nitrate Sr(NO3)2, and ammonium niobium oxalate C4H4NNbO9.nH2O according to the chemical formula of the material, and add them to an appropriate amount of water. Heat and stir at 85 °C until completely dissolved to obtain a metal ion solution. During the process, use H2O2 to oxidize the oxalate ions to ensure the dissolution of Nb 5+ Dissolution, slowly add EDTA acid and citric acid, and adjust the pH of the solution with ammonia water. Continuously heat and stir until the solution becomes gel-like. After placing it in the drying oven and presenting a black fluffy shape, take out the sample and heat it in a flat furnace to burn off the organic matter. After stirring until there are no sparks, put it into a low-temperature muffle furnace for heat preservation to obtain the preliminary powder. Weigh the corresponding content of cobalt nitrate hexahydrate (Co(NO3)2·6H2O), put it into an ethanol solution, and grind it to accelerate its dissolution. Then soak the prepared initial powder in the cobalt nitrate solution. The obtained mixture is stirred, ground, and dried in an agate mortar to obtain the final powder.

[0027] Mix the powder with the binder PVA at 1 wt% and grind it evenly in an agate mortar. After drying in the drying oven, grind it again until it is fine. Weigh a certain amount of powder according to a 0.5 mm membrane thickness and place it in a stainless steel mold. After spreading it evenly, keep it under pressure at 150 - 200 MPa for 2 - 3 min in an infrared press to obtain a formed green body. Then place it on an alumina plate and put it into a muffle furnace for sintering to densification using a two-step sintering technique. After raising the temperature to 1100 °C, keep it warm for 10 min, and then quickly cool it to 1050 °C at a rate of 10 °C·min -1 Rate, and keep it warm for a long time during the remaining time, where the total heat preservation time is 5 h. Subsequently, cool it at a rate of 2 °C·min -1The rate is cooled down to 200 °C to ensure that the membrane has optimal mechanical properties.

[0028] As Figure 1 shown, for the XRD patterns of the dual-phase oxygen permeable membrane samples with different Sr contents (0.4, 0.5, 0.6) prepared in this example, all samples are composed of two phases, fluorite and perovskite. The XRD diffraction peaks of each material can be assigned to the main diffraction positions of the two constituent phases. With the increase of Sr content at the A site, the perovskite structure is maintained.

[0029] As Figure 2 shown, for the surface microtopography of several dual-phase membrane samples prepared in this example and the EDS distribution of some elements corresponding to the 2Co-SDC-SSCFN6 sample. Several composite membrane materials are sintered densely, the grains are arranged closely, and there are obvious separated crystalline phases. The larger grains are the SDC fluorite phase, and the smaller grains are Sm 1-x Sr x Cu 0.2 Fe 0.7 Nb 0.1 O 3-δ perovskite phase, and a connected network for ion and electron transport is constructed between the two phases. Figure 2 The distribution of elements in (d) corresponds to the two-phase distribution. Among them, the distribution profile of Ce element in the fluorite phase, and the distribution profiles of Sr and Fe elements in the perovskite are consistent with the two-phase grain distribution. Co element is uniformly distributed on the entire membrane surface. Due to the low addition content and the limitation of resolution, the presence of cobalt oxide particles is not detected in the SEM test either. It can be seen from the EDS image that there is still a certain self-diffusion between the two-phase elements. Some metal elements such as Cu and Fe are dissolved into the SDC lattice, which will also promote the performance of the dual-phase membrane.

[0030] As Figure 3 shown, for the 2Co-SDC-SSCFN6 dual-phase membrane prepared by different powder synthesis methods in this example, the oxygen permeation rate as a function of temperature and the corresponding Arrhenius relationship. All oxygen fluxes are obtained under stable conditions. It can be seen that the preparation method has a significant impact on the oxygen permeation rate of the dual-phase membrane. Especially for the dual-phase membrane prepared by the sol-gel method, its oxygen permeation rate is significantly higher than that of the solid-state reaction method. Among them, the sample prepared by the one-pot method has the highest oxygen permeation rate. The difference in oxygen permeation rate is due to the higher uniformity of the membrane prepared by the sol-gel method. The more uniform the two phases are, the higher the oxygen permeation rate is.

[0031] As Figure 4As shown in the figure, the morphology of the 2Co-SDC-SSCF dual-phase oxygen permeable membrane prepared in this example and the surface / line scan element distribution in some regions in the high-angle annular dark field (HAADF-STEM) mode. The uniform distribution of Co elements indicates that the added sintering aid elements may exist in both phases, partially dissolve into the SDC lattice at high temperatures, and at the same time, some Co elements at the grain boundaries will also partially enter the SSCF perovskite lattice.

[0032] As Figure 5 shown in the figure, for the fitting relationship of the oxygen permeation rate of the dual-phase membranes with different mass ratios of the two phases prepared in this example, according to the fitting function relationship, the extreme point exists at the position where the mass ratio of the two phases is 1.408. Therefore, the best performance of the studied dual-phase oxygen permeable membrane is obtained when the mass ratio of the fluorite and perovskite phases is 58.47:41.53.

[0033] As Figure 6 shown in the figure, for the relationship between the oxygen permeation flux and the reciprocal of the thickness of the dual-phase membranes prepared in this example at different temperatures, it can be seen that when the thickness is greater than 0.5 mm, / lg ( P h / P l ) shows a linear relationship with 1 / L. When the membrane thickness is reduced to a small enough value, surface oxygen exchange will become a key factor. As shown in the figure, when the membrane thickness is less than 0.5 mm, the oxygen permeability deviates from the linear trend and increases slowly. Therefore, it can be concluded that when the thickness of the studied dual-phase membrane is less than 0.5 mm, the surface exchange process cannot be ignored, and when the thickness is greater than 0.5 mm, volume diffusion is the rate-limiting step of oxygen permeation.

[0034] As Figure 7 shown in the figure, for the XRD patterns on the air side and the purge side of the 58.47wt%SDC(Co)-41.53wt%SSCFN6 prepared in this example after long-term stability testing, the basic phase structures of fluorite and perovskite are maintained on both sides of the membrane. It is worth noting that no diffraction peak of CuO is detected on the air side. This indicates that the increase in Sr content leads to the elimination of the separated CuO particles.

[0035] As Figure 8 shown in the figure, for the schematic diagrams of the traditional sintering process and two sintering techniques in this example. In the TSS process, after raising the temperature to T1, hold for 10 min, and then rapidly cool to T2 at a rate of 10 °C·min -1 and hold for a long time for the remaining time, where the total holding time is 5 h. By changing the values of T1 (1100 °C and 1250 °C) and T2 (950 °C, 1000 °C, 1050 °C, and 1100 °C), different sintering regimes are determined.

[0036] As Figure 9 shown, for this embodiment, the test image of the Vickers hardness of the dual-phase oxygen permeable membrane was taken using a touch screen microhardness tester (MHV-1000Z). The cross-shaped indentation is within the red frame.

[0037] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A novel high-throughput dual-phase oxygen permeable membrane material resistant to CO2, characterized in that: The high-throughput novel dual-phase oxygen permeable membrane material resistant to CO2 is 58.47wt% SDC(Co) - 41.53wt% Sm 0.4 Sr 0.6 Cu 0.2 Fe 0.7 Nb 0.1 O 3-δ 。 2. A novel high-throughput dual-phase oxygen permeable membrane material resistant to CO2 according to claim 1, characterized in that: The perovskite phase of a novel high-throughput dual-phase oxygen permeable membrane material resistant to CO2 is based on SrFeO with mixed ionic and electronic conduction 3-δ in the ABO3-type perovskite oxide of the SrFeO-based, and is double-doped at the B-site with 2+ Cu 5+ and Nb 3. A novel high-flux dual-phase oxygen-permeable membrane material resistant to CO2 according to claim 1, characterized in that: The fluorite phase of the novel high-throughput dual-phase oxygen permeable membrane material resistant to CO2 is based on Ce 0.8 Sm 0.2 O 2-δ On this basis, Co element with a content of 1.5 - 2.5 mol% is added in the way of preferential segregation at grain boundaries.

4. A novel high-flux dual-phase oxygen permeable membrane material resistant to CO2 according to claim 1, characterized in that: The mass ratio of the fluorite phase to the perovskite phase of the high-throughput novel dual-phase oxygen permeable membrane material resistant to CO2 is 55 - 60:40 - 45.

5. A novel high-flux dual-phase oxygen permeable membrane material resistant to CO2 according to claim 1, characterized in that: The Sr content at the A site in the perovskite phase of the high-throughput novel dual-phase oxygen permeable membrane material resistant to CO2 is 0.

6.

6. The preparation method of a novel high-flux dual-phase oxygen permeable membrane material resistant to CO2 according to any one of claims 1-5, characterized in that: It includes the following steps: S1: Weigh the metal nitrates contained in the perovskite phase and the metal nitrates contained in the fluorite phase respectively and place them in deionized water. Heat and stir them respectively. After complete dissolution, add complexing agents to obtain metal ion solutions. Roast the preliminary fluorite-phase powder and the preliminary perovskite-phase powder. Add the sintering aid element Co in the form of grain boundary preferential segregation. Finally, grind them respectively to obtain the perovskite-phase powder and the fluorite-phase powder; S2: Granulate and dry-press the perovskite-phase powder and the fluorite-phase powder prepared in step S1, and then sinter them densely in a high-temperature muffle furnace.

7. The preparation method of a novel high-flux dual-phase oxygen permeable membrane material resistant to CO2 according to claim 6, characterized in that: The metal nitrates contained in the perovskite phase in step S1 include cerium salt, samarium salt, iron salt, strontium salt, niobium salt, and copper salt; The metal nitrates contained in the fluorite phase in step S1 include cerium salt, samarium salt, iron salt, strontium salt, niobium salt, and copper salt; The heating and stirring in step S1 include stirring at 70 - 90 °C until complete dissolution, and adding H2O2 during stirring; The complexing agents in step S1 include EDTA acid and citric acid, and the pH of the solution is adjusted with ammonia water to obtain the metal ion solution; Adding the sintering aid element Co in the form of grain boundary preferential segregation in step S1 includes weighing the corresponding content of cobalt nitrate hexahydrate (Co(NO3)2·6H2O), putting it into an ethanol solution, grinding it, then soaking the prepared initial powder in the cobalt nitrate solution, and stirring, grinding, and drying the obtained mixture in an agate mortar to obtain the final powder.

8. The preparation method of a novel high-flux dual-phase oxygen permeable membrane material resistant to CO2 according to claim 7, characterized in that: The cerium salt includes cerium nitrate hexahydrate; The samarium salt includes samarium nitrate hexahydrate; The copper salt includes copper nitrate; The iron salt includes iron nitrate nonahydrate; The strontium salt includes strontium nitrate; The niobium salt includes ammonium niobium oxalate.

9. The preparation method of a novel high-flux dual-phase oxygen permeable membrane material resistant to CO2 according to claim 7, characterized in that: In step S2, it is sintered densely by adopting a two-step sintering technique in a high-temperature muffle furnace. After the temperature is raised to 1080 - 1120 °C, it is kept warm for 8 - 12 min, and then rapidly cooled to 1000 - 1050 °C at a rate of 8 - 12 °C·min -1 The rate is rapidly cooled to 1000 - 1050 °C, and kept warm for a long time during the remaining time, where the total heat preservation time is 4 - 6 h, and then cooled to 190 - 210 °C at a rate of 1 - 3 °C·min -1 The rate is cooled to 190 - 210 °C.

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