High-entropy perovskite membrane and application in oxygen separation and membrane reactor

A perovskite, high-entropy technology, used in semi-permeable membrane separation, separation methods, dispersed particle separation, etc., can solve the problem of low metal ion diffusion rate, unsatisfactory oxygen permeability performance and stability, and hinder mixed conductor oxygen permeation membrane. Technical application and other issues, to achieve the effect of reducing the diffusion rate of metal ions, promoting the formation of fast oxygen ions and electron channels, excellent oxygen permeability and thermal stability

Active Publication Date: 2022-01-25
JIANGNAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

(2) Hysteretic diffusion effect, due to the difference in the type of metal ions, the diffusion process needs to be carried out across a large range of lattice barriers, resulting in a low diffusion rate of metal ions
However, in terms of membrane catalytic reactions, the current research still faces many difficulties, mainly including the oxygen permeability of membrane materials and the reaction atmosphere (especially reducing and CO 2 atmosphere) under thermochemical stability, which seriously hinders the practical application of mixed conductor oxygen permeable membrane technology in related membrane reactors
Therefore, the existing membrane materials cannot meet the requirements of the actual membrane reaction process in terms of oxygen permeability and stability. Oxygen membrane materials, seeking breakthroughs in oxygen permeability and thermochemical stability

Method used

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  • High-entropy perovskite membrane and application in oxygen separation and membrane reactor
  • High-entropy perovskite membrane and application in oxygen separation and membrane reactor
  • High-entropy perovskite membrane and application in oxygen separation and membrane reactor

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Preparation of the invention (LA) with solid phase reaction method (LA 0.2 PR 0.2 ND 0.2 BA 0.2 SR 0.2 (Co) 0.8 FE 0.2 ) O 3-δ Take a sample, the chemical measurement of materials will be purchased by LA (CO) 3 ) 3 PR 2 (Co 3 ) 3 ND 2 O 3 , Baco 3 , SRCO 3 , CO 2 O 3 , Fe 2 O 3 After the powder was precisely mixed, anhydrous ethanol was added, placed in a ball mill, wet grinding 8h, and the rotational speed was 500 rpm. The mixture after wet milling was placed in an oven, and the dried powder was placed in a high temperature muffle furnace, and the particle diameter was calcined in a 950 ° C air atmosphere. After grinding, the particle size was about 800 nm (LA) 0.2 PR 0.2 ND 0.2 BA 0.2 SR 0.2 (Co) 0.8 FE 0.2 ) O 3-δ Pre-generic powder.

[0036] The powder was pressed into a membrane green body by a stainless steel mold having an inner diameter of 14 mm, and the heating rate was controlled at 1 ° C / min, and the film green body was tied to room temperature at a rate of 1.5...

Embodiment 2

[0041] Preparation of a material (LAPRCABASR) by solid phase reaction method 0.2 (Co 0.8 FE 0.2 ) O 3-δ Take a sample, the chemical measurement of materials will be purchased by LA (CO) 3 ) 3 PR 2 (Co 3 ) 3 Caco 3 , Baco 3 , SRCO 3 , CO 2 O 3 , Fe 2 O 3 After the powder is exactly mixed, anhydrous ethanol is added, placed in a ball mill, and the rotational speed is 550 rpm, and then dried in a static air, and the dried powder is placed in a high temperature muffle, calcined in an air atmosphere at 1000 ° C for 8 h After grinding, the particle size is approximately 2 μm (LAPRCABASR) 0.2 (Co 0.8 FE 0.2 ) O 3-δ Pre-generic powder.

[0042] The powder was pressed into a film green body under 18 mPa pressure by a stainless steel mold having an inner diameter of 14 mm, and the heating rate was controlled to 3 ° C / min, and the film green body was sintered at 1250 ° C for 10 h, and the rate of 3 ° C / min was lowered to room temperature, That is, the slice film (the thickness of the fil...

Embodiment 3

[0046] Preparation of a material (LAPRCABASR) by solid phase reaction method 0.2 (CoCrfemnni) 0.2 O 3-δ Take an example, the chemical measurement of materials will be purchased by LA (CO) 3 ) 3 PR 2 (Co 3 ) 3 Caco 3 , Baco 3 , SRCO 3 , CO 2 O 3 , Cr 2 O 3 , Fe 2 O 3 After the MnO, NiO powder is precisely mixed, anhydrous ethanol is added, placed in a ball mill 12h, rotation speed of 600 rpm, and then dried in static air, put the dry powder into a high temperature muffle, at 1250 ° C Calcination of 7 h in the air atmosphere, after standing to room temperature, after grinding, the particle size is about 5 μm (LAPRCABASR) 0.2(CoCrfemnni) 0.2 O 3-δ Pre-generic powder.

[0047] The powder was pressed into a membrane green body under 18 MPa pressure by a stainless steel mold having an inner diameter of 14 mm, and the heating rate was controlled to 4 ° C / min, and the film green body was sintered at 1200 ° C for 12 h, and the rate of 2 ° C / min was lowered to room temperature, That is,...

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Abstract

The invention discloses a high-entropy perovskite membrane and application in oxygen separation and membrane reactors, and belongs to the field of mixed conductor high-entropy perovskite membrane materials. According to the high-entropy perovskite membrane material, the high-entropy perovskite membrane has a general formula (Ax1A'x2... A<(m-1)>'xm)(By1B'y2... B<(n-1)>'yn) O3-delta, at least one of site A and site B is a multi-element with five or more elements, delta is oxygen lattice defect number, A is one or more of alkali metal, alkaline earth metal or rare earth metal elements, B is one or more of transition metal elements, x1 +... + xm is equal to 1, y1 +... + yn1 is equal to 1, delta is more than or equal to 0 and less than 3, and the material is prepared by using a solid-phase reaction method. The membrane material provided by the invention can effectively improve the thermal stability and oxygen permeability of the material, also has excellent CO2 resistance, can be applied for a long time in the fields of oxygen separation and membrane reactors, and meets the requirements of industrial application.

Description

Technical field [0001] The present invention relates to the field of high entropy of the hybrid conductor, and more particularly to a high entropy calcium titanium ore film and its application in oxygen separation and membrane reactors. Background technique [0002] The high entropy oxide is different from the traditional doped oxide design concept, and the design concept of high entropy alloy is expanded to the perovskite oxide, which is composed of at least five oxides to equimola or near Moore ratio. The type entropy is greater than 1.5R, and its tissue and properties have a large difference in tissue compared to traditional perovskite oxides. Similar to high entropy alloys, high-entropy calcium titanium ore oxides also have similar "four effects": (1) high entropy effect, high-imperient entropy And the multi-component system can significantly reduce the freedom of forming solid solution phase, and also makes the system high thermal stability. (2) Hysteresis diffusion effect, ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01D69/02B01D69/06B01D69/08B01D69/04B01D67/00B01D53/22
CPCB01D69/02B01D69/06B01D69/08B01D69/04B01D67/0041B01D53/228
Inventor 朱佳伟李禹锡蒋逸鸣陈明法
Owner JIANGNAN UNIV
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