阅读说明：本技术 一种具有耐二氧化碳的、高稳定性的含铋双相混合导体透氧膜材料及其制备方法 (Carbon dioxide-resistant high-stability bismuth-containing two-phase mixed conductor oxygen-permeable membrane material and preparation method thereof ) 是由 罗惠霞 张超 黄彦昊 曾令勇 何溢懿 于 2021-08-04 设计创作，主要内容包括：本发明设计和制备了一种具有耐二氧化碳的、高稳定性的含铋双相混合导体透氧膜材料,属于无机功能陶瓷制造技术领域。该含铋双相混合导体透氧膜材料的通式为Ce-(0.9)Pr-(0.1)O-(2-δ)-Pr-(0.6)Sr-(0.4)Fe-(1-x)Bi-(x)O-(3-δ)(CPO-PSF-(1-x)B-(x)O；x＝0.01,0.025,0.05,0.10,0.15,0.20)；首先通过“溶胶-凝胶一锅法”制备粉体,将粉体在马弗炉中950℃下煅烧12小时得到前驱体粉末,然后将前驱体粉末压片烧结,得到最后所需的混合导体透氧膜。通过调控Bi元素与Fe元素的比例,从而得到所需的含铋双相混合导体透氧膜材料。本发明制备的透氧膜材料在氦气/二氧化碳等气体吹扫下具有良好稳定性,且在二氧化碳腐蚀性气氛下透氧量损失较小。本发明可以作为新型气体分离材料和碳捕捉材料应用于高温复杂气氛用氧行业,例如富氧燃烧,水分解及甲烷偶联等领域。(The invention designs and prepares a bismuth-containing two-phase mixed conductor oxygen-permeable membrane material with carbon dioxide resistance and high stability, belonging to the technical field of inorganic functional ceramic manufacture. The general formula of the bismuth-containing two-phase mixed conductor oxygen-permeable membrane material is Ce 0.9 Pr 0.1 O 2‑δ ‑Pr 0.6 Sr 0.4 Fe 1‑x Bi x O 3‑δ (CPO‑PSF 1‑x B x O; x is 0.01, 0.025, 0.05, 0.10, 0.15, 0.20); firstly, preparing powder by a sol-gel one-pot method, calcining the powder in a muffle furnace at 950 ℃ for 12 hours to obtain precursor powder, and tabletting the precursor powderSintering to obtain the final required mixed oxygen permeable membrane for conductor. The required Bi-phase mixed conductor oxygen permeable membrane material containing bismuth is obtained by regulating and controlling the proportion of Bi element and Fe element. The oxygen permeable membrane material prepared by the invention has good stability under the sweeping of gases such as helium/carbon dioxide and the like, and has small oxygen permeation loss under the corrosive atmosphere of carbon dioxide. The invention can be used as a novel gas separation material and a carbon capture material to be applied to the oxygen industry in high-temperature complex atmosphere, such as the fields of oxygen-enriched combustion, water decomposition, methane coupling and the like.)

1. A bismuth-containing two-phase mixed conductor oxygen-permeable membrane material with carbon dioxide resistance and high stability is characterized by having the following chemical formula and weight percentage:

60wt.％Ce_0.9Pr_0.1O_2-δ-40wt.％Pr_0.6Sr_0.4Fe_1-xBi_xO_3-δ(x＝0.01，0.025，0.05，0.10，0.15，0.20)。

2. a bismuth-containing two-phase mixed conductor oxygen-permeable membrane material with carbon dioxide resistance and high stability is characterized by comprising the following processes and steps:

(a) ce is weighed in turn according to the stoichiometric ratio_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_1-xBi_xO_3-δDissolving the corresponding nitrate in deionized water, stirring thoroughly until it is dissolved, adding citric acid monohydrate as chelating agent and ethylene glycol as dispersant into beaker, wherein the metal ions and citric acid in the solutionThe mass ratio of the ethylene glycol is 1: 2;

(b) stirring the solution until the solution becomes clear and transparent, placing a beaker on a heating type magnetic stirrer, continuously heating and evaporating until the solution is converted into gel, putting the gel into an oven at 140 ℃ for drying for 24 hours to obtain dry gel, fully grinding the gel, then putting the gel into a crucible, and keeping the temperature at 600 ℃ for 8 hours to calcine and remove organic matters;

(c) grinding the obtained powder, putting the powder into a crucible, and calcining the powder at 950 ℃ for 10 hours to obtain Ce_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_{1- x}Bi_xO_3-δThe powder of (4);

(d) and (2) pressing the powder at 10MPa to obtain a cake-shaped sheet body, slowly heating the sheet body to 1400 ℃ (x is 0.01, 0.025 and 0.05) and 1350 ℃ (x is 0.10 and 0.15) and 1300 ℃ (x is 0.20) at the speed of 1 ℃/min, calcining for 5 hours, sintering to obtain a compact two-phase mixed conductor oxygen permeable membrane, and polishing by sand paper to obtain the high-stability bismuth-containing mixed conductor oxygen permeable membrane.

3. The solution of claim 2 wherein the mass ratio of metal ions, citric acid, and glycol is 1: 2.

4. Ce according to claim 2_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_1-xBi_xO_3-δThe sintering temperatures were 1400 ℃ (x ═ 0.01, 0.025, 0.05), and 1350 ℃ (x ═ 0.10, 0.15), 1300 ℃ (x ═ 0.20).

5. The 1400 ℃ (x-0.01, 0.025, 0.05), and 1350 ℃ (x-0.10, 0.15), 1300 ℃ (x-0.20) calcination procedure according to claim 2: the heating rate is 1 ℃ per minute, the heat preservation time is 300 minutes, and the cooling rate is 1 ℃ per minute.

6. The bismuth-containing two-phase mixed conductor oxygen permeable membrane material with high stability and carbon dioxide resistance, which is prepared according to the method in the claims 1-2, is used for performance analysis of stability.

Technical Field

The invention belongs to the technical field of functional ceramic manufacture, and particularly relates to a chemical component Ce_0.9Pr_0.1O_2-δ-Pr_0.6Sr_{0 4}Fe_1-xBi_xO_3-δA two-phase mixed conductor oxygen permeable membrane material and a preparation method thereof.

Background

The mixed conductor oxygen permeable membranes (OTMs) are environment-friendly and efficient air separation membranes, can effectively separate oxygen and capture carbon dioxide, and have certain catalytic activity. A perovskite membrane is an example of a dense ceramic membrane, and has both oxygen ion and electron conductivity under medium-high temperature conditions, so that oxygen can be permeated with high selectivity by the action of an oxygen concentration gradient, and high-purity oxygen can be produced continuously at low cost. The mixed conductor oxygen permeable membrane has great potential in the aspects of oxygen-enriched combustion, methane Partial Oxidation (POM), water decomposition hydrogen production coupling and the like, wherein the oxygen permeable membrane for oxygen-enriched combustion resists CO₂Stability is an important measure.

Most oxygen permeable membranes containing alkali metal elements (e.g., Ba) in the A-site are exposed to high temperature CO₂The carbonate impurity phase is easily formed in the atmosphere, and the stability and the oxygen permeability of the membrane body material are reduced. The oxygen permeable membrane containing Co element at the B site has larger expansion coefficient at high temperature, and the structural stability of the oxygen permeable membrane material is reduced.

In order to increase the stability of mixed oxygen-permeable conductor membrane materials as much as possible while maintaining high oxygen permeability, many efforts have been made by researchers. Firstly, La, Pr and other rare earth metal cations are partially doped with alkali metal elements at A site, and the content of Co element in B site is reduced, Caro et al research Pr_0.6Sr_0.4Co_xFe_1-xO_3-δ(x is more than or equal to 0 and less than or equal to 1), the stability of the Co-free system is proved to be stronger, and then the system passes through the fluorite phase which resists the carbon dioxide atmosphere and the calciumCoupling of titanium ore, development of Ce_{0 9}Pr_0.1O_2-δ- Pr_0.6Sr_0.4FeO_3-δThe two-phase oxygen permeable membrane further improves the stability, but has lower oxygen permeability. Du et al developed Ce_0.9La_0.1O_2-δ-La_0.6Sr_0.4FeO_3-δOxygen permeable membranes, available at 900 ℃ CO₂Keeping 0.2mL cm under atmosphere^-2min^-1Oxygen permeability of more than 15 hours. Recently, Rohuxia topic group has developed Ce by partially replacing the original transition metal component in the B site with a more acidic (less basic) or more stable transition metal component_{0 9}Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_1-xAl_xO_3-δ、Ce_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_1-xIn_xO_3-δAnd Ce_0.85Pr_0.1Cu_0.05O_2-δ-Pr_0.6Sr_0.4Fe_1-xCu_xO_3-δThe system of the equal two-phase mixed conductor oxygen-permeable membrane material can reach 1mL cm^-2min^-1And the oxygen permeation quantity is kept for more than 100 hours.

Bi element is in the fifth main group of the sixth period, and the outer electron arrangement is 4f¹⁴5d¹⁰6s²6p³However, since two electrons of the 6s orbital are hardly lost due to the inert electron effect caused by the strong penetration effect of the 6s orbital, Bi³⁺Doping to the B site can create oxygen vacancies, similar to the Fe, Al, and In elements, for valence stabilization. Bismuth oxide delta-Bi at high temperatures₂O₃The oxygen-permeable membrane contains a large number of oxygen vacancies, is an excellent oxygen ion conductor and is beneficial to the diffusion and transmission of oxygen in the oxygen-permeable membrane. In addition, Bi₂O₃Also frequently used as catalysts, e.g. Liu et al by nano-Bi₂O₃Catalytic electrolytic reduction of CO₂For HCOOH, this catalytic activity is more advantageous for use in carbon capture. Shao et al have studied BaBi_xCo_0.2Fe_0.8-xO_3-δThe single-phase oxygen permeable membrane can reach 0.8mL cm^-2min^-1The above mentionedOxygen content, but poor stability. Therefore, the invention discloses a bismuth-containing two-phase mixed conductor oxygen permeable membrane material Ce with carbon dioxide resistance and high stability_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_1-xBi_xO_3-δ(CPO-PSF_1-xB_xO，x＝0.01，0.025，0.05，0.10，0.15， 0.20)。

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a bismuth-containing two-phase mixed conductor oxygen-permeable membrane material with carbon dioxide resistance and high stability and a preparation method thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

a bismuth-containing two-phase mixed conductor oxygen-permeable membrane material with carbon dioxide resistance and high stability has the following composition:

Ce_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_1-xBi_xO_3-δ(x＝0.01，0.025，0.05，0.10，0.15，0.20)

a preparation method of a bismuth-containing two-phase mixed conductor oxygen-permeable membrane material with carbon dioxide resistance and high stability comprises the following process steps:

(1) ce is weighed in turn according to the stoichiometric ratio_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_1-xBi_xO_3-δDissolving the corresponding nitrate in deionized water, fully stirring until the nitrate is dissolved, and adding citric acid monohydrate serving as a chelating agent and glycol serving as a dispersing agent into a beaker, wherein the mass ratio of metal ions, citric acid and glycol in the solution is 1: 2;

(2) stirring the solution until the solution becomes clear and transparent, placing a beaker on a heating type magnetic stirrer, continuously heating and evaporating until the solution is converted into gel, putting the gel into an oven at 140 ℃ for drying for 24 hours to obtain dry gel, fully grinding the dry gel, putting the gel into a crucible, keeping the temperature at 600 ℃ for 8 hours, and calcining the gel to remove organic matters;

(3) grinding the powder, placing the powder into a crucible at 950 DEG CCalcining for 10h to obtain Ce_0.9Pr_0.1O_2-δ-Pr_0.6Sr_{0 4}Fe_{1- x}Bi_xO_3-δThe powder of (4);

(4) and (2) pressing the powder at 10MPa to obtain a cake-shaped sheet body, slowly heating the sheet body to 1400 ℃ (x is 0.01, 0.025 and 0.05) and 1350 ℃ (x is 0.10 and 0.15) and 1300 ℃ (x is 0.20) at the speed of 1 ℃/min, calcining for 5 hours, sintering to obtain a compact two-phase mixed conductor oxygen permeable membrane, and polishing by using abrasive paper to obtain the bismuth-containing mixed conductor oxygen permeable membrane with high stability and small oxygen permeability loss under a carbon dioxide atmosphere.

Compared with the prior art, the bismuth-containing two-phase mixed conductor oxygen permeable membrane material prepared by the technology has compact surface, no obvious cracks, defects and through holes, excellent mechanical property and capability of being applied to He/CO₂And the like in low-oxygen corrosive atmosphere for 50 hours. Meanwhile, the biphase mixed conductor oxygen permeable membrane material containing bismuth prepared by the technology has good oxygen permeability. For example, 0.6mm of the mixed conductor oxygen permeable membrane material Ce_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_0.99Bi_0.01O_3-δUnder the working condition of 1000 ℃ with helium as purge gas, 0.71mL cm can be obtained^-2min^-1And the oxygen permeation rate is kept constant for 50 h.

Drawings

FIG. 1 shows Ce prepared by the method of the present invention_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_1-xBi_xO_3-δ(x ═ 0.01, 0.025, 0.05, 0.10, 0.15, 0.20) room temperature XRD pattern of bismuth-containing two-phase mixed conductor oxygen permeable membrane powder;

FIG. 2 shows Ce prepared by the method of the present invention_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_1-xBi_xO_3-δ(x ═ 0.01, 0.025, 0.05, 0.10, 0.15, 0.20) XRD refinement results of bismuth-containing two-phase mixed conductor oxygen-permeable membrane powder;

FIG. 3 shows Ce prepared by the method of the present invention_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_1-xBi_xO_3-δ(x ═ 0.01, 0.025, 0.05, 0.10, 0.15, 0.20) SEM pictures of bi-phase mixed conducting oxygen permeable membrane materials containing bismuth;

FIG. 4 shows Ce prepared by the method of the present invention_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_1-xBi_xO_3-δ(x is 0.01, 0.025, 0.05, 0.10, 0.15, 0.20) BSEM photograph of Bi-phase mixed conductor oxygen permeable membrane material

FIG. 5 shows Ce prepared by the method of the present invention_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_1-xBi_xO_3-δ(x is 0.01, 0.025, 0.05, 0.20) the oxygen permeability of the bi-phase mixed conductor oxygen permeable membrane material containing bismuth changes with temperature when He is used as purge gas.

FIG. 6 shows Ce prepared by the method of the present invention_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_1-xBi_xO_3-δ(x is 0.01, 0.025, 0.05, 0.20) bismuth-containing two-phase mixed oxygen-permeable membrane material prepared from CO₂Oxygen permeability as a sweep gas varies with temperature.

FIG. 7 shows Ce prepared by the method of the present invention_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_1-xBi_xO_3-δ(x ═ 0.01, 0.025, 0.05, 0.10.0.15, 0.20) XRD results of bismuth-containing two-phase mixed conductor oxygen-permeable membrane powders calcined at 800 ℃ in Ar atmosphere for 24 hours.

FIG. 8 shows Ce prepared by the method of the present invention_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_1-xBi_xO_3-δ(x is 0.01, 0.025, 0.05, 0.10.0.15, 0.20) XRD result of bismuth-containing two-phase mixed conductor oxygen permeable membrane powder calcined in Ar atmosphere at 900 ℃ for 24 h.

FIG. 9 shows Ce prepared by the method of the present invention_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_1-xBi_xO_3-δ(x ═ 0.01, 0.025, 0.05, 0.10, 0.15, 0.20) bismuth-containingAnd (3) XRD result of calcining the biphase mixed conductor oxygen-permeable membrane powder for 24 hours at 1000 ℃ in Ar atmosphere.

FIG. 10 shows Ce prepared by the method of the present invention_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_1-xBi_xO_3-δ(x is 0.01, 0.025, 0.05, 0.10, 0.15, 0.20) Bi-containing two-phase mixed oxygen-permeable membrane powder for conductor at 800 deg.C in CO₂XRD results after calcination in atmosphere for 24 hours.

FIG. 11 shows Ce prepared by the method of the present invention_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_1-xBi_xO_3-δ(x is 0.01, 0.025, 0.05, 0.10, 0.15, 0.20) Bi-containing two-phase mixed oxygen-permeable membrane powder for conductor at 900 deg.C in CO₂XRD results after calcination in atmosphere for 24 h.

FIG. 12 shows Ce prepared by the method of the present invention_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_1-xBi_xO_3-δ(x is 0.01, 0.025, 0.05, 0.10, 0.15, 0.20) Bi-containing two-phase mixed oxygen-permeable membrane powder for conductor at 1000 deg.C for CO₂XRD results after calcination in atmosphere for 24 h.

FIG. 13 shows Ce prepared by the method of the present invention_0.9Pr_0.1O_2-δ-Pr_{0 6}Sr_{0 4}Fe_1-xBi_xO_3-δx is 0.01, 0.025, 0.05, 0.10, 0.15, 0.20) EDS photograph of Bi-phase mixed conductor oxygen permeable membrane material

FIG. 14 shows Ce prepared by the method of the present invention_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_1-xBi_xO_3-δ(x is 0.01, 0.025, 0.05) Bi-phase mixed conductor oxygen permeable membrane containing bismuth has oxygen permeability stability curve with time under 1000 ℃.

Detailed Description

The invention will be further elucidated by means of the following figures and examples, without the scope of protection of the invention being limited to the ones shown.

Example 1:

accurately weigh 4.1057g Ce(NO₃)₃·6H₂O，1.8656g Pr(NO₃)₃·6H₂O，2.1336g Fe(NO₃)₃·9H₂O. 0.4538g Sr(NO₃)₂，0.0261g Bi(NO₃)₃·5H₂O, 8.7669g of citric acid monohydrate, stirring the solution until the solution becomes clear and transparent, placing a beaker on a magnetic stirrer, continuously heating and evaporating until the solution becomes gel, then putting the gel into an oven at 140 ℃ for drying for 24 hours to obtain fluffy dry gel, fully grinding the gel, putting the gel into a crucible, keeping the temperature at 600 ℃ for 8 hours, and calcining to remove organic matters. Fully grinding the calcined powder, putting the powder into a crucible, and calcining the powder for 10 hours at 950 ℃ to obtain Ce_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_0.99Bi_0.01O_3-δThe powder is pressed into a cake-shaped sheet body under the pressure of 10MPa, the sheet body is slowly heated up to 1400 ℃ and calcined for 5 hours to be sintered to obtain a compact two-phase ceramic oxygen permeable membrane material, and the compact two-phase mixed conductor oxygen permeable membrane containing bismuth is obtained by sanding.

Example 2:

4.1057g Ce (NO) were accurately weighed₃)₃·6H₂O，1.8514g Pr(NO₃)₃·6H₂O，2.0800g Fe(NO₃)₃·9H₂O， 0.4492g Sr(NO₃)₂，0.0647g Bi(NO₃)₃·5H₂O, 8.7669g of citric acid monohydrate, stirring the solution until the solution becomes clear and transparent, placing a beaker on a magnetic stirrer, continuously heating and evaporating until the solution becomes gel, then putting the gel into an oven at 140 ℃ for drying for 24 hours to obtain fluffy dry gel, fully grinding the gel, putting the gel into a crucible, keeping the temperature at 600 ℃ for 8 hours, and calcining to remove organic matters. Fully grinding the calcined powder, putting the powder into a crucible, and calcining the powder for 10 hours at 950 ℃ to obtain Ce_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_0.975Bi_0.025O_3-δPressing the powder under 10MPa to obtain cake-shaped sheet bodies, slowly heating the sheet bodies, calcining at 1400 ℃ for 5 hours, and sintering to obtain compact two-phase ceramicThe oxygen membrane material is polished by abrasive paper to obtain the high-stability bi-phase mixed conductor oxygen permeable membrane containing bismuth.

Example 3:

4.1057g Ce (NO) were accurately weighed₃)₃·6H₂O，1.8283g Pr(NO₃)₃·6H₂O，1.9932g Fe(NO₃)₃·9H₂O， 0.4418g Sr(NO₃)₂，0.1272g Bi(NO₃)₃·5H₂O, 8.7669g of citric acid monohydrate, stirring the solution until the solution becomes clear and transparent, placing a beaker on a magnetic stirrer, continuously heating and evaporating until the solution becomes gel, then putting the gel into an oven at 140 ℃ for drying for 24 hours to obtain fluffy dry gel, fully grinding the gel, putting the gel into a crucible, keeping the temperature at 600 ℃ for 8 hours, and calcining to remove organic matters. Fully grinding the calcined powder, putting the powder into a crucible, and calcining the powder for 10 hours at 950 ℃ to obtain Ce_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_0.95Bi_0.05O_3-δThe powder is pressed into a cake-shaped sheet body under the pressure of 10MPa, the sheet body is slowly heated up to 1400 ℃ and calcined for 5 hours to be sintered to obtain a compact two-phase ceramic oxygen permeable membrane material, and the compact two-phase mixed conductor oxygen permeable membrane containing bismuth is obtained by sanding.

Example 4:

4.1057g Ce (NO) were accurately weighed₃)₃·6H₂O，1.7844g Pr(NO₃)₃·6H₂O，1.8277g Fe(NO₃)₃·9H₂O. 0.4276g Sr(NO₃)₂，0.2463g Bi(NO₃)₃·5H₂O, 8.7669g of citric acid monohydrate, stirring the solution until the solution becomes clear and transparent, placing a beaker on a magnetic stirrer, continuously heating and evaporating until the solution becomes gel, then putting the gel into an oven at 140 ℃ for drying for 24 hours to obtain fluffy dry gel, fully grinding the gel, putting the gel into a crucible, keeping the temperature at 600 ℃ for 8 hours, and calcining to remove organic matters. Fully grinding the calcined powder, putting the powder into a crucible, and calcining the powder for 10 hours at 950 ℃ to obtain Ce_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_0.9Bi_0.1O_3-δThe powder is pressed into a cake-shaped sheet body under the pressure of 10MPa, the sheet body is slowly heated up and calcined for 5 hours at 1350 ℃ to be sintered to obtain a compact two-phase ceramic oxygen permeable membrane material, and the compact two-phase mixed conductor oxygen permeable membrane containing bismuth is obtained by sanding.

Example 5:

4.1057g Ce (NO) were accurately weighed₃)₃·6H₂O，1.7433g Pr(NO₃)₃·6H₂O，1.6725g Fe(NO₃)₃·9H₂O， 0.4143g Sr(NO₃)₂，0.3579g Bi(NO₃)₃·5H₂O, 8.7669g of citric acid monohydrate, stirring the solution until the solution becomes clear and transparent, placing a beaker on a magnetic stirrer, continuously heating and evaporating until the solution becomes gel, then putting the gel into an oven at 140 ℃ for drying for 24 hours to obtain fluffy dry gel, fully grinding the gel, putting the gel into a crucible, keeping the temperature at 600 ℃ for 8 hours, and calcining to remove organic matters. Fully grinding the calcined powder, putting the powder into a crucible, and calcining the powder for 10 hours at 950 ℃ to obtain Ce_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_0.85Bi_0.15O_3-δThe powder is pressed into a cake-shaped sheet body under the pressure of 10MPa, the sheet body is slowly heated up and calcined for 5 hours at 1350 ℃ to be sintered to obtain a compact two-phase ceramic oxygen permeable membrane material, and the compact two-phase mixed conductor oxygen permeable membrane containing bismuth is obtained by sanding.

Example 6:

4.1057g Ce (NO) were accurately weighed₃)₃·6H₂O，1.7046g Pr(NO₃)₃·6H₂O，1.5267g Fe(NO₃)₃·9H₂O. 0.4018g Sr(NO₃)₂，0.4629g Bi(NO₃)₃·5H₂O, 8.7669g of citric acid monohydrate, stirring the solution until the solution becomes clear and transparent, placing a beaker on a magnetic stirrer, continuously heating and evaporating until the solution becomes gel, then putting the gel into an oven at 140 ℃ for drying for 24 hours to obtain fluffy dry gel, fully grinding the gel, putting the gel into a crucible, keeping the temperature at 600 ℃ for 8 hours, and calcining to remove organic matters.Fully grinding the calcined powder, putting the powder into a crucible, and calcining the powder for 10 hours at 950 ℃ to obtain Ce_0.9Pr_0.1O_2-δ-Pr_0.6Sr_0.4Fe_0.8Bi_0.2O_3-δThe powder is pressed into a cake-shaped sheet body under the pressure of 10MPa, the sheet body is slowly heated up and calcined for 5 hours at 1300 ℃ to be sintered to obtain a compact two-phase ceramic oxygen permeable membrane material, and the compact two-phase mixed conductor oxygen permeable membrane containing bismuth is obtained by sanding.

Evaluation experiment:

when the air flow is 150mL min^-1Purge gas 49mL min^-1He+1mL min^-1Ne，60wt.％ Ce_0.9Pr_0.1O_2-δ-40wt.％Pr_0.6Sr_0.4Fe_0.99Bi_0.01O_3-δ0.71mL cm was obtained at 1000 ℃^-2min^-1The oxygen permeability of the system can stably exist for more than 50 hours in a complex working environment atmosphere, and the performance is not reduced.