Bismuth-containing biphase mixed conductor oxygen permeation membrane material with carbon dioxide resistance and high stability and preparation method thereof

Abstract

The invention designs and prepares a bismuth-containing biphase mixed conductor oxygen permeation membrane material with carbon dioxide resistance and high stability, and belongs to the technical field of inorganic functional ceramic manufacturing. The general formula of the bismuth-containing biphase mixed conductor oxygen permeation membrane material is Ce[0.9]Pr[0.1]O[2-delta]-Pr[0.6]Sr[0.4]Fe[1-x]Bi[x]O[3-delta] (CPO-PSF[1-x]B[x]O; x is equal to 0.01, 0.025, 0.05, 0.10, 0.15 or 0.20). The preparation method comprises the steps: firstly, preparing powder by a sol-gel one-pot method, calcining the powder in a muffle furnace at the temperature of 950 DEG C for 12 hours to obtain precursor powder, and then tabletting and sintering the precursor powder to obtain the required mixed conductor oxygen permeation membrane. The required bismuth-containing biphase mixed conductor oxygen permeation membrane material is obtained by regulating and controlling the ratio of the Bi element to the Fe element. The prepared oxygen permeation membrane material has good stability under purging of helium / carbon dioxide and other gases, and the oxygen permeation amount loss is small under the carbon dioxide corrosive atmosphere. The material can be used as a novel gas separation material and a carbon capture material to be applied to the high-temperature complex atmosphere oxygen industry, such as the fields of oxygen-enriched combustion, water decomposition, methane coupling and the like.

Description

technical field

[0001] The invention belongs to the technical field of functional ceramics manufacturing, in particular to a chemical composition Ce 0.9 PR 0.1 o 2-δ -Pr 0.6 Sr 0 4 Fe 1-x Bi x o 3-δ Two-phase mixed conductor oxygen-permeable membrane material and its preparation method. Background technique

[0002] Mixed conductor oxygen permeable membranes (OTMs) are environmentally friendly and efficient air separation membranes, which can effectively separate oxygen and capture carbon dioxide, and possess certain catalytic activity. As a kind of dense ceramic film, take perovskite film as an example, it has both oxygen ion and electronic conductivity under medium and high temperature conditions, so it can permeate oxygen with high selectivity under the action of oxygen concentration gradient, thus continuous, Low-cost production of high-purity oxygen. Mixed conductor oxygen-permeable membranes have great potential in the coupling of oxygen-rich combustion, parti...

Examples

Embodiment 1

[0032] Accurately weigh 4.1057g Ce(NO 3 ) 3 ·6H 2 O, 1.8656g Pr(NO 3 ) 3 ·6H 2 O, 2.1336g Fe(NO 3 ) 3 9H 2 O. 0.4538g Sr(NO 3 ) 2 , 0.0261g Bi(NO 3 ) 3 ·5H 2 O, 8.7669g citric acid monohydrate, stir the solution until it becomes clear and transparent, place the beaker on a magnetic stirrer, continue heating and evaporating until it turns into a gel, and then put the gel in an oven at 140 ° C for 24 hours to obtain The dry gel is fluffy, and after being fully ground, it is put into a crucible and kept at 600°C for 8 hours for calcination to remove organic matter. The calcined powder is fully ground and placed in a crucible, and calcined at 950°C for 10 hours to obtain Ce 0.9 PR 0.1 o 2-δ -Pr 0.6 Sr 0.4 Fe 0.99 Bi 0.01 o 3-δ The powder is pressed at 10MPa to obtain a cake-shaped sheet, and the sheet is slowly heated up at 1400°C for 5 hours and sintered to obtain a dense dual-phase ceramic oxygen-permeable membrane material, and sanded to obtain a high-stabil...

Embodiment 2

[0034] Accurately weigh 4.1057g Ce(NO 3 ) 3 ·6H 2 O, 1.8514g Pr(NO 3 ) 3 ·6H 2 O, 2.0800g Fe(NO 3 ) 3 9H 2 O, 0.4492g Sr(NO 3 ) 2 , 0.0647g Bi(NO 3 ) 3 ·5H 2 O, 8.7669g citric acid monohydrate, stir the solution until it becomes clear and transparent, place the beaker on a magnetic stirrer, continue heating and evaporating until it turns into a gel, and then put the gel in an oven at 140 ° C for 24 hours to obtain The dry gel is fluffy, and after being fully ground, it is put into a crucible and kept at 600°C for 8 hours for calcination to remove organic matter. The calcined powder is fully ground and placed in a crucible, and calcined at 950°C for 10 hours to obtain Ce 0.9 PR 0.1 o 2-δ -Pr 0.6 Sr 0.4 Fe 0.975 Bi 0.025 o 3-δ The powder is pressed at 10MPa to obtain a cake-shaped sheet, and the sheet is slowly heated up at 1400°C for 5 hours and sintered to obtain a dense dual-phase ceramic oxygen-permeable membrane material, and sanded to obtain a high-stab...

Embodiment 3

[0036] Accurately weigh 4.1057g Ce(NO 3 ) 3 ·6H 2 O, 1.8283g Pr(NO 3 ) 3 ·6H 2 O, 1.9932g Fe(NO 3 ) 3 9H 2 O, 0.4418g Sr(NO3 ) 2 , 0.1272g Bi(NO 3 ) 3 ·5H 2 O, 8.7669g citric acid monohydrate, stir the solution until it becomes clear and transparent, place the beaker on a magnetic stirrer, continue heating and evaporating until it turns into a gel, and then put the gel in an oven at 140°C for 24 hours to obtain The dry gel is fluffy, and after being fully ground, it is put into a crucible and kept at 600°C for 8 hours for calcination to remove organic matter. The calcined powder is fully ground and placed in a crucible, and calcined at 950°C for 10 hours to obtain Ce 0.9 PR 0.1 o 2-δ -Pr 0.6 Sr 0.4 Fe 0.95 Bi 0.05 o 3-δ The powder is pressed at 10MPa to obtain a cake-shaped sheet, and the sheet is slowly heated at 1400°C for 5 hours to sinter to obtain a dense dual-phase ceramic oxygen-permeable membrane material, and sanded to obtain a high-stability bismut...

technical field

[0001] The invention belongs to the technical field of functional ceramics manufacturing, in particular to a chemical composition Ce 0.9 PR 0.1 o 2-δ -Pr 0.6 Sr 0 4 Fe 1-x Bi x o 3-δ Two-phase mixed conductor oxygen-permeable membrane material and its preparation method. Background technique

[0002] Mixed conductor oxygen permeable membranes (OTMs) are environmentally friendly and efficient air separation membranes, which can effectively separate oxygen and capture carbon dioxide, and possess certain catalytic activity. As a kind of dense ceramic film, take perovskite film as an example, it has both oxygen ion and electronic conductivity under medium and high temperature conditions, so it can permeate oxygen with high selectivity under the action of oxygen concentration gradient, thus continuous, Low-cost production of high-purity oxygen. Mixed conductor oxygen-permeable membranes have great potential in the coupling of oxygen-rich combustion, parti...

Examples

Embodiment 1

[0032] Accurately weigh 4.1057g Ce(NO 3 ) 3 ·6H 2 O, 1.8656g Pr(NO 3 ) 3 ·6H 2 O, 2.1336g Fe(NO 3 ) 3 9H 2 O. 0.4538g Sr(NO 3 ) 2 , 0.0261g Bi(NO 3 ) 3 ·5H 2 O, 8.7669g citric acid monohydrate, stir the solution until it becomes clear and transparent, place the beaker on a magnetic stirrer, continue heating and evaporating until it turns into a gel, and then put the gel in an oven at 140 ° C for 24 hours to obtain The dry gel is fluffy, and after being fully ground, it is put into a crucible and kept at 600°C for 8 hours for calcination to remove organic matter. The calcined powder is fully ground and placed in a crucible, and calcined at 950°C for 10 hours to obtain Ce 0.9 PR 0.1 o 2-δ -Pr 0.6 Sr 0.4 Fe 0.99 Bi 0.01 o 3-δ The powder is pressed at 10MPa to obtain a cake-shaped sheet, and the sheet is slowly heated up at 1400°C for 5 hours and sintered to obtain a dense dual-phase ceramic oxygen-permeable membrane material, and sanded to obtain a high-stabil...

Embodiment 2

[0034] Accurately weigh 4.1057g Ce(NO 3 ) 3 ·6H 2 O, 1.8514g Pr(NO 3 ) 3 ·6H 2 O, 2.0800g Fe(NO 3 ) 3 9H 2 O, 0.4492g Sr(NO 3 ) 2 , 0.0647g Bi(NO 3 ) 3 ·5H 2 O, 8.7669g citric acid monohydrate, stir the solution until it becomes clear and transparent, place the beaker on a magnetic stirrer, continue heating and evaporating until it turns into a gel, and then put the gel in an oven at 140 ° C for 24 hours to obtain The dry gel is fluffy, and after being fully ground, it is put into a crucible and kept at 600°C for 8 hours for calcination to remove organic matter. The calcined powder is fully ground and placed in a crucible, and calcined at 950°C for 10 hours to obtain Ce 0.9 PR 0.1 o 2-δ -Pr 0.6 Sr 0.4 Fe 0.975 Bi 0.025 o 3-δ The powder is pressed at 10MPa to obtain a cake-shaped sheet, and the sheet is slowly heated up at 1400°C for 5 hours and sintered to obtain a dense dual-phase ceramic oxygen-permeable membrane material, and sanded to obtain a high-stab...

Embodiment 3

[0036] Accurately weigh 4.1057g Ce(NO 3 ) 3 ·6H 2 O, 1.8283g Pr(NO 3 ) 3 ·6H 2 O, 1.9932g Fe(NO 3 ) 3 9H 2 O, 0.4418g Sr(NO3 ) 2 , 0.1272g Bi(NO 3 ) 3 ·5H 2 O, 8.7669g citric acid monohydrate, stir the solution until it becomes clear and transparent, place the beaker on a magnetic stirrer, continue heating and evaporating until it turns into a gel, and then put the gel in an oven at 140°C for 24 hours to obtain The dry gel is fluffy, and after being fully ground, it is put into a crucible and kept at 600°C for 8 hours for calcination to remove organic matter. The calcined powder is fully ground and placed in a crucible, and calcined at 950°C for 10 hours to obtain Ce 0.9 PR 0.1 o 2-δ -Pr 0.6 Sr 0.4 Fe 0.95 Bi 0.05 o 3-δ The powder is pressed at 10MPa to obtain a cake-shaped sheet, and the sheet is slowly heated at 1400°C for 5 hours to sinter to obtain a dense dual-phase ceramic oxygen-permeable membrane material, and sanded to obtain a high-stability bismut...

Images