A non-metal ion-doped lanthanum tungstate-type mixed proton-electron conductor hydrogen permeable material and its preparation method and application

An ion doping, electronic conductor technology, applied in separation methods, chemical instruments and methods, gas treatment, etc., can solve the problems of low hydrogen permeability and insufficient stability, and achieve small particle diameter, long-term stable operation, and powder. The effect of low phase formation temperature

Active Publication Date: 2021-05-14
SOUTH CHINA UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In general, materials such as lanthanum tungstate mixed conductor hydrogen permeable membranes have low hydrogen permeation performance, and their long-term operation stability is insufficient in a hydrogen-containing atmosphere.

Method used

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  • A non-metal ion-doped lanthanum tungstate-type mixed proton-electron conductor hydrogen permeable material and its preparation method and application
  • A non-metal ion-doped lanthanum tungstate-type mixed proton-electron conductor hydrogen permeable material and its preparation method and application
  • A non-metal ion-doped lanthanum tungstate-type mixed proton-electron conductor hydrogen permeable material and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] A phosphorus ion-doped lanthanum tungstate-based mixed proton-electron conductor hydrogen permeable material La 5.5 W 0.75 P 0.25 o 12-δ (δ = 0.5) (LWP25) and undoped lanthanum tungstate based mixed proton-electron conductor material La 5.5 WO 12-δ (δ = 0.4) (LWO), such as figure 1 Shown, preparation method comprises the following steps:

[0036] (1) Weigh LWP25 raw material: 12.334g La 2 o 3 Dissolved in concentrated nitric acid with a mass fraction of 65%, 2.553g WO 3 Soluble in ammonia water with a mass fraction of 18%, 0.317g NH 4 h 2 PO 4 Dissolve in deionized water, mix the three evenly, add 8.56g glycine to the mixture;

[0037] (2) Weigh LWO raw material: 11.916g La 2 o 3 Dissolved in concentrated nitric acid with a mass fraction of 65%, 3.083g WO 3 Dissolved in ammoniacal liquor with a mass fraction of 18%, the two are mixed evenly, and 8.65g of glycine is added in the mixed solution;

[0038] (3) Heat the nitrate mixture obtained in steps (1)...

Embodiment 2

[0046] A sulfide-doped lanthanum tungstate-based mixed proton-electron conductor hydrogen permeable material Nd of the present embodiment 5.3 W 0.9 S 0.1 o 12-δ (δ = 1) (NWS10) The preparation method includes the following steps:

[0047] (1) Weigh NWP10 raw material: 8.01g Nd 2 o 3 Dissolved in concentrated nitric acid with a mass fraction of 65%, 1.87g WO 3 Soluble in ammonia water with a mass fraction of 18%, 0.103g NH 4 h 2 SO 4 Dissolve in deionized water, mix the three evenly, add 5.56g glycine to the mixture;

[0048] (2) Heat the nitrate mixture obtained in step (1) to 300°C and stir for 24 hours until the solution becomes gel-like, then put the gel into an electric furnace, heat to 150°C and bake to obtain the precursor of the powder ; Put the powder in a muffle furnace, heat it at a rate of 3° C. to 1000° C. per minute for 5 hours, and obtain the powder NWS10.

[0049] (3) Weigh 2g of phase-forming powder NWS10 and put it into a cast iron mold, keep it un...

Embodiment 3

[0052] A phosphorus ion-doped lanthanum tungstate-based mixed proton-electron conductor hydrogen permeable material Eu 5.7 W 0.5 P 0.5 o 12-δ (δ = 0) (EuWP50) preparation method includes the following steps:

[0053] (1) Weigh EWP50 raw material: 10.43g Eu 2 o 3 Dissolved in concentrated nitric acid with a mass fraction of 65%, 1.21g WO 3 Soluble in ammonia water with a mass fraction of 18%, 0.59g NH 4 h 2 PO 4 Dissolve in deionized water, mix the three evenly, add 6.45g glycine to the mixture;

[0054] (2) Heat the nitrate mixture obtained in step (1) to 220°C and stir for 28 hours until the solution takes on the form of a gel, then put the gel into an electric furnace, heat to 250°C and bake to obtain the precursor of the powder ; The powder is placed in a muffle furnace, and the temperature is kept at a rate of 1.5°C to 900°C per minute for 7.5h to obtain the powder EuWP50.

[0055] (3) Weigh 1.8g of phase-forming powder EuWP50 and put it into a cast iron mold, ...

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Abstract

The invention discloses a non-metal ion-doped lanthanum tungstate-type mixed proton-electron conductor hydrogen permeable material, a preparation method and application thereof. The general chemical formula of the material is Ln a W 1‑x m x o 12‑δ , where Ln is one of the lanthanides La, Nd, Eu, Er; M is one of the non-metallic elements P and S; δ is a non-stoichiometric ratio; 0≤δ≤1, 5.3≤a≤5.7,0 ≤x≤0.5. The material of the present invention can be prepared by glycine-nitrate combustion method. In the material of the present invention, the electrical conductivity of the membrane material is improved by the doping of non-metal ions, so that the hydrogen permeability of the membrane material is improved. Moreover, the material has good operational stability in a hydrogen-containing atmosphere, and can be used to separate hydrogen from a hydrogen-containing mixed gas.

Description

technical field [0001] The invention belongs to the technical field of application of hydrogen separation materials, and in particular relates to a non-metal ion-doped lanthanum tungstate-type mixed proton-electron conductor hydrogen permeable material and its preparation method and application. Background technique [0002] Hybrid proton-electron conductor hydrogen permeable material is an inorganic dense ceramic material, which has a selectivity of up to 100% for hydrogen at high temperature due to its simultaneous proton and electronic conductivity. In addition, using it in a series of hydrogen-related reactions can effectively improve the efficiency of the reaction and the utilization rate of energy. Therefore, hybrid proton-electron conductor hydrogen permeable materials have been extensively studied. [0003] Since 1970 La 2 o 3 -WO 3 Since the phase equilibrium of the system was studied, lanthanum tungstate oxides have attracted much attention. Haugsrud et al. st...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01D53/22C04B35/495C04B35/447C04B35/624C04B35/626C04B35/622
CPCB01D53/228B01D2256/16C04B35/447C04B35/495C04B35/622C04B35/624C04B35/6267C04B35/62675C04B2235/3224C04B2235/3227C04B2235/3258C04B2235/447C04B2235/448C04B2235/6562C04B2235/6565
Inventor 王海辉庄丽彬薛健
Owner SOUTH CHINA UNIV OF TECH
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