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Oxide-doped medium-low temperature mixed conducting oxygen-permeable membrane material and its preparation method

A technology of mixed conductors and oxides, which is applied in the field of medium and low temperature mixed conductor oxygen permeable membrane materials and their preparation, can solve problems such as affecting the oxygen flux and stability of materials, achieve high chemical and structural stability, improve stability, The effect of meeting the requirements of medium and low temperature operation

Inactive Publication Date: 2012-03-07
NANJING UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

At present, the materials that can meet this requirement are basically cobalt-containing materials, such as SrCo 0.8 Fe 0.2 o 3-δ , but this kind of material is prone to phase transition under the conditions of medium and low temperature and low oxygen partial pressure, which seriously affects the oxygen flux and stability of the material

Method used

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  • Oxide-doped medium-low temperature mixed conducting oxygen-permeable membrane material and its preparation method
  • Oxide-doped medium-low temperature mixed conducting oxygen-permeable membrane material and its preparation method
  • Oxide-doped medium-low temperature mixed conducting oxygen-permeable membrane material and its preparation method

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Experimental program
Comparison scheme
Effect test

Embodiment 1～5

[0021] Preparation of Perovskite Oxide SrCo by Solid State Reaction Method 0.8 Fe 0.2 o 3-δ (-0.50.8 Fe 0.2 o 3-δ -Nb 2 o 5 (-0.53 、Co 2 o 3 and Fe 2 o 3 After the powders were mixed, ethanol was added, placed in a ball mill for wet grinding for 36 hours at a speed of 350 rpm, and then dried in static air. Put the dried powder in a high-alumina crucible and bake it in an air atmosphere at 900°C for 5 hours to obtain SrCo 0.8 Fe 0.2 o 3-δ (SCF) powder. Will Nb 2 o 5 0.5, 1, 3, 5, 10% of the total mass of the oxygen permeable membrane material and SrCo 0.8 Fe 0.2 o 3-δ Mix, add ethanol, and place in a ball mill for ball milling at a speed of 400 rpm for 8 hours. After ball milling, the powder is fully dried in air at 120°C. Put the dried powder in a corundum crucible and bake it in an air atmosphere at 950°C for 5 hours to obtain SrCo 0.8 Fe 0.2 o 3-δ -Nb 2 o 5 The powders are represented by SCFNb0.5, SCFNb1, SCFNb3, SCFNb5, and SCFNb10 respectively.

[0...

Embodiment 6

[0024] The perovskite material SrCo 0.8 Fe 0.2 o 3-δ Materials and Nb 2 o 5 Doped example 1-5 material SrCo 0.8 Fe 0.2 o 3-δ -Nb 2 o 5 X-ray diffraction tests were carried out by figure 2 (a) It can be seen that the materials SCF and SCFNb both form a complete perovskite phase, and no significant change is found in the main perovskite phase of the material before and after doping. The study found that the material has no obvious second phase or the impurity phase generated by the phase reaction is one of the prerequisites to ensure the material has a high oxygen flux. And in the material of the present invention, Nb 2 o 5 It has a high solid solution limit (greater than 10%) in the main phase of SCF, and the prepared material has no obvious impurity phase, which predicts to a certain extent that Nb 2 o 5 The effect on the oxygen flux of the host phase SCF is relatively small. figure 2 (b) is the XRD pattern of the material after being treated in He atmosphere a...

Embodiment 7

[0026] For the perovskite material SrCo 0.8 Fe 0.2 o 3-δ Materials and Nb 2 o 5 Doped (Example 1-5 doping amount is 0.5, 1, 3, 5, 10% by mass percentage) the material SrCo of the present invention 0.8 Fe 0.2 o 3-δ -Nb 2 o 5 The oxygen permeability performance at different temperatures was tested (the thickness of the membrane is 1mm, the air flow rate on the feed side is 100ml / min, and the helium flow rate on the permeation side is 30ml / min), and compared with the material SrCo reported in the literature. 0.8 Fe 0.2 o 3-δ -Al 3 o 3 For comparison (membrane thickness is 1mm, feed side air flow is 100ml / min, permeate side helium flow is 30ml / min). see results image 3 .

[0027] Depend on image 3 It can be seen that a small amount of transition metal element oxide Nb 2 o 5 (0.5%) can significantly improve the oxygen permeability of the material, and the oxygen flux of SCFNb0.5 at 900 ° C is as high as 3.37ml / (cm 2 min), suitable for applications in oxygen sepa...

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Abstract

The invention relates to an oxide-doped medium-low temperature mixed conducting oxygen-permeable membrane material and its preparation method. The material provided by the invention is a composition of a perovskite oxide and a simple metal oxide. The general formula of the perovskite oxide is C1-xC'xDyD'1-yO3-delta, wherein x is less than 1 and greater than or equal to 0; y is less than 1 and greater than or equal to 0; delta is less than 0.5 and greater than minus 0.5; C and C' both contain any one element selected from La, Pr, Nd, Sm, Gd, Ba or Sr; D and D' both contain any one element selected from Cr, Mn, Fe, Co, Ni, Cu, Zn or Bi. The simple metal oxide is one component selected from the group consisting of vanadium oxide, niobium oxide, thallium oxide, chrome oxide or molybdena. The weight of the doped simple oxides accounts for 0.01-15% the gross weight of the composition. According to the oxygen-permeable membrane material provided by the invention, the stability of a host material can be greatly raised at low oxygen partial pressure by a few doped simple oxides, and high oxygen permeable capability of the material can be maintained. The preparation method provided by the invention endows the material with more excellent medium-low temperature performance, is applicable to be operated at low oxygen partial pressure for a long time, and meets the requirement of large-scale industrial application.

Description

technical field [0001] The invention relates to a medium-low temperature mixed conductor oxygen-permeable membrane material and a preparation method thereof, in particular to an oxide-doped medium-low temperature mixed conductor oxygen-permeable membrane material and a preparation method thereof. technical background [0002] The mixed conductor membrane material is an inorganic ceramic membrane material that can simultaneously conduct electrons and oxygen ions (Teraoka et al., Chem. Lett., 1985), and is widely used in pure oxygen preparation, fuel cells, sensors, membrane reactors, etc. fields. Utilizing its 100% selectivity for oxygen ions, it can be used to produce high-purity oxygen (>99%). At the same time, the mixed conductor membrane material has a high oxygen flux, so the traditional air is replaced by the mixed conductor oxygen permeable membrane. Separation methods (such as cryogenic separation) can save nearly one third of investment and operating costs. Howe...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C04B35/01C04B35/32C04B35/622
Inventor 金万勤张广儒刘郑堃董学良徐南平
Owner NANJING UNIV OF TECH
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