新型掺杂钙钛矿型混合导体透氧膜材料的研究
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摘要
钙钛矿型致密透氧膜作为一类重要的无机膜,在高温气体分离和膜催化反应中有巨大的潜在研究价值。在纯氧制备、燃料电池以及化学反应器等方面有着十分诱人的应用前景。对于面向应用的透氧膜材料而言,提高膜的氧通量、解决低氧分压气氛中膜的稳定性等问题是其实现工业化应用的关键,但是从该类材料目前的研究现状来看,同时满足以上要求的透氧膜材料还是很少。为此,开发高氧透量、高稳定性的混合导体透氧膜材料是现目前亟待解决的关键问题,本论文的研究工作正是顺应这种要求而展开的。
我们在前人实验的基础上,借助于X射线衍射(XRD),扫描电子显微镜-元素分析(SEM-EDX),热重-示差量热(TG-DSC),程序升温氧脱附(O2-TPD),程序升温氢还原(H2-TPR)等分析测试手段对钙钛矿型混合导体膜的性能材料的优化及开发作了一些新的探索。
针对在实验过程中遇到的问题,由于锆(Zr)的熔点较高,使得BaCo0.4Fe0.4Zr0.2O3-δ钙钛矿烧结温度较高,同时锆(Zr)的离子半径比较大,较难进入到立方钙钛矿的晶格中以至于很难形成纯相钙钛矿结构,我们通过采用具有稳定化学价态且离子半径较小的锌(Zn)逐步取代BaCo0.4Fe0.4Zr0.2O3-δ体系中的锆(Zr)来制备BaCo0.4Fe0.4ZnxZr0.2-xO3-δ(0≤x≤0.2)系列钙钛矿,通过XRD表征证明离子半径较小的Zn离子取代BaCo0.4Fe0.4Zr0.2O3-δ结构中离子半径较大的Zr离子,有利于改善钙钛矿相结构,避免生成杂相,同时通过O2-TPD测试表明BaCo0.4Fe0.4Zn0.2O3-δ在高温下低氧分压气氛中具有良好的结构稳定性。我们对BaCo0.4Fe0.4Zn0.2O3-δ膜片进行透氧性能研究测试,在Air/He梯度950 oC下,厚度为0.56 mm的膜片透氧量高达0.9 ml/min.cm2 (6.72×10-7 mol/cm2.s),通过Kim等人提出的扩散理论设计实验,实验结果表明BaCo0.4Fe0.4Zn0.2O3-δ膜片在厚度大于或等于0.56 mm情况下,透氧控制步骤为体相扩散过程,依据Wagner方程拟合数据作图发现在温度为900 oC附近,BaCo0.4Fe0.4Zn0.2O3-δ膜片的透氧控制步骤为体相扩散控制。在长达100小时的透氧测试过程没有发现透氧量有明显的下降,且通过对反应后的膜片的XRD分析表明膜片仍保持完整的钙钛矿结构。
对具有高氧渗透能力的钙钛矿氧化物SrCo(1-y)TayO3-δ(y=0.0, 0.01, 0.05, 0.1, 0.2, 0.3)中钽掺杂对相结构、高温氧脱附(O2-TPD)、高温氢还原(H2-TPR)和氧渗透性能的影响进行研究,结果表明,随着钽掺杂量的增加,SrCo(1-y)TayO3-δ的室温钙钛矿相结构发生了六方相—立方钙钛矿相—立方钙钛矿相+Brownmillerite相的变化,并得出SrCo0.9Ta0.1O3-δ的钙钛矿结构是最优的立方钙钛矿结构。紧接着我们对SrCo0.9Ta0.1O3-δ钙钛矿膜进行了SEM-EDX表征,发现通过等静压煅烧法可以制备致密的透氧膜,且膜片表面和截面的元素计量比符合SrCo0.9Ta0.1O3-δ钙钛矿的化学计量比,随后对膜片进行了透氧性能测试,研究结果表明在700– 950 oC温度范围内,在Air/He梯度下,SrCo0.9Ta0.1O3-δ膜片具有可观的透氧量,厚度为0.65 mm的膜片在950 oC下,透氧量高达2.07 ml/min.cm2 (1.63×10-6 mol/cm2.s)。另外通过模型理论分析发现,在膜片厚度大于0.65 mm,反应温度在900 -950 oC之间时,透氧过程主要受体相扩散控制。在长达520小时的透氧测试过程没有发现透氧量有明显的下降,透量能基本维持在1.70 - 1.96 ml/min·cm2之间,利用XRD表征手段对新鲜膜片和长期稳定性测试后的膜片进行了对比分析,发现长时间稳定操作后的SrCo0.9Ta0.1O3-δ膜片仍保持完整的钙钛矿结构,没有发生本质的变化,表现出优异的结构稳定性和足够的机械性能,是一种有潜在应用前景的透氧膜材料。
As a very important inorganic membrane, perovskite-type dense oxygen permeable membranes have great potential applications in high temperature gas separation and membrane catalytic reaction research. Specically, perovskite-type dense oxygen permeable membranes are promising in producing pure oxygen, cathode for SOFC (solid oxide fuel cell) and chemical reactor. For practical application, these materials were required to have high oxygen permeability as well as sustainable structural stability to withstand harsh conditions. However, the present perovskite-type mixed-conducting oxides either showed high oxygen permeability but with poor structural and thermochemical stability in reducing atmosphere or showed high stability but poor oxygen permeation ability, and ideal materials are very few, therefore, it is a critical problem to develop novel materials both with high oxygen permeability and high structure stability, and this is also my thesis’s purpose.
Based on the previous work, the present study was to exploited new mixed-conducting perovksite-type membrane materials for oxygen permeation with the aids of XRD, SEM-EDX, TG-DSC, O2-TPD and H2-TPR analysis.
It was found that it was difficult to synthesize the pure phase BaCo0.4Fe0.4Zr0.2O3-δsince the Zr4+ ion is relatively large for the occupation of the B-site of the perovskite structure, therefore Zn which exhibits constant state was chosen to substitute Zr in BaCo0.4Fe0.4Zr0.2O3-δperovskite, From the XRD analysis, it is proved that the doping of B site of the perovskite structure with a divalent metal like zinc leads to the elimination of nonstoichiometric oxygen variations and lattice expansion of oxygen,from the O2-TPD it can be seen that BaCo0.4Fe0.4Zn0.2O3-δperovskite keep very good structure stability under high temperature and low oxygen partial pressure. Oxygen permeation test was investigated by the gas chromatography, an oxygen permeation flux of 0.9 ml/min.cm2 (6.72×10-7 mol/cm2.s) was found at 950 ?C with a membrane thickness of 0.56 mm. It was also found out that the oxygen permeation was controlled by the bulk diffusion under the experimental conditions. The membrane was steadily operated for more than 100 h in the oxygen permeation test. The XRD analysis after long term test proved that membrane still kept perovskite structure without been destroyed.
The effects of Ta ion doping on the structure,high temperature oxygen desorption(O2-TPD), high temperature hydrogen reduction and oxygen transporting properties of SrCo(1-y)TayO3-δ(y=0.0, 0.01, 0.05, 0.1, 0.2, 0.3)were investigated. The perovskite phase structure of the as prepared SrCo(1-y)TayO3-δwas shown to change in the sequence of the hexagonal– cubic– cubic + browmnillerite as Ta ion content y increased. It was found that SrCo0.9Ta0.1O3-δpossessed the most optimized perovskite phase structure. The SrCo0.9Ta0.1O3-δmembrane was investigated by SEM-EDX analysis, it was found that membrane was dense and the compositions both on the surface and the cross agreed with SrCo0.9Ta0.1O3-δstoichiometry. Oxygen permeation test was performed within the temperature range of 700 - 950 oC, and the oxygen permeation flux of 2.07 ml/min·cm2 (1.63×10-6 mol/cm2.s)was obtained at 950°C with a thickness of 0.65 mm. It was found that the oxygen permeation of SrCo0.9Ta0.1O3-δmembrane disk were controlled by the bulk diffusion under the research conditions. The oxygen permeation fluxes varied within a very narrow range, i.e., from 1.70 to 1.96 ml/min·cm2 in the entire 520 h long-term operation. The XRD analysis of the spent membrane showed that the perovskite structure had been well preserved after the long-term permeation test both in the air feed gas side and He sweep gas side which indicated that SrCo0.9Ta0.1O3-δceramic membrane was a promising material used in high-temperature oxygen separation.
我们在前人实验的基础上,借助于X射线衍射(XRD),扫描电子显微镜-元素分析(SEM-EDX),热重-示差量热(TG-DSC),程序升温氧脱附(O2-TPD),程序升温氢还原(H2-TPR)等分析测试手段对钙钛矿型混合导体膜的性能材料的优化及开发作了一些新的探索。
针对在实验过程中遇到的问题,由于锆(Zr)的熔点较高,使得BaCo0.4Fe0.4Zr0.2O3-δ钙钛矿烧结温度较高,同时锆(Zr)的离子半径比较大,较难进入到立方钙钛矿的晶格中以至于很难形成纯相钙钛矿结构,我们通过采用具有稳定化学价态且离子半径较小的锌(Zn)逐步取代BaCo0.4Fe0.4Zr0.2O3-δ体系中的锆(Zr)来制备BaCo0.4Fe0.4ZnxZr0.2-xO3-δ(0≤x≤0.2)系列钙钛矿,通过XRD表征证明离子半径较小的Zn离子取代BaCo0.4Fe0.4Zr0.2O3-δ结构中离子半径较大的Zr离子,有利于改善钙钛矿相结构,避免生成杂相,同时通过O2-TPD测试表明BaCo0.4Fe0.4Zn0.2O3-δ在高温下低氧分压气氛中具有良好的结构稳定性。我们对BaCo0.4Fe0.4Zn0.2O3-δ膜片进行透氧性能研究测试,在Air/He梯度950 oC下,厚度为0.56 mm的膜片透氧量高达0.9 ml/min.cm2 (6.72×10-7 mol/cm2.s),通过Kim等人提出的扩散理论设计实验,实验结果表明BaCo0.4Fe0.4Zn0.2O3-δ膜片在厚度大于或等于0.56 mm情况下,透氧控制步骤为体相扩散过程,依据Wagner方程拟合数据作图发现在温度为900 oC附近,BaCo0.4Fe0.4Zn0.2O3-δ膜片的透氧控制步骤为体相扩散控制。在长达100小时的透氧测试过程没有发现透氧量有明显的下降,且通过对反应后的膜片的XRD分析表明膜片仍保持完整的钙钛矿结构。
对具有高氧渗透能力的钙钛矿氧化物SrCo(1-y)TayO3-δ(y=0.0, 0.01, 0.05, 0.1, 0.2, 0.3)中钽掺杂对相结构、高温氧脱附(O2-TPD)、高温氢还原(H2-TPR)和氧渗透性能的影响进行研究,结果表明,随着钽掺杂量的增加,SrCo(1-y)TayO3-δ的室温钙钛矿相结构发生了六方相—立方钙钛矿相—立方钙钛矿相+Brownmillerite相的变化,并得出SrCo0.9Ta0.1O3-δ的钙钛矿结构是最优的立方钙钛矿结构。紧接着我们对SrCo0.9Ta0.1O3-δ钙钛矿膜进行了SEM-EDX表征,发现通过等静压煅烧法可以制备致密的透氧膜,且膜片表面和截面的元素计量比符合SrCo0.9Ta0.1O3-δ钙钛矿的化学计量比,随后对膜片进行了透氧性能测试,研究结果表明在700– 950 oC温度范围内,在Air/He梯度下,SrCo0.9Ta0.1O3-δ膜片具有可观的透氧量,厚度为0.65 mm的膜片在950 oC下,透氧量高达2.07 ml/min.cm2 (1.63×10-6 mol/cm2.s)。另外通过模型理论分析发现,在膜片厚度大于0.65 mm,反应温度在900 -950 oC之间时,透氧过程主要受体相扩散控制。在长达520小时的透氧测试过程没有发现透氧量有明显的下降,透量能基本维持在1.70 - 1.96 ml/min·cm2之间,利用XRD表征手段对新鲜膜片和长期稳定性测试后的膜片进行了对比分析,发现长时间稳定操作后的SrCo0.9Ta0.1O3-δ膜片仍保持完整的钙钛矿结构,没有发生本质的变化,表现出优异的结构稳定性和足够的机械性能,是一种有潜在应用前景的透氧膜材料。
As a very important inorganic membrane, perovskite-type dense oxygen permeable membranes have great potential applications in high temperature gas separation and membrane catalytic reaction research. Specically, perovskite-type dense oxygen permeable membranes are promising in producing pure oxygen, cathode for SOFC (solid oxide fuel cell) and chemical reactor. For practical application, these materials were required to have high oxygen permeability as well as sustainable structural stability to withstand harsh conditions. However, the present perovskite-type mixed-conducting oxides either showed high oxygen permeability but with poor structural and thermochemical stability in reducing atmosphere or showed high stability but poor oxygen permeation ability, and ideal materials are very few, therefore, it is a critical problem to develop novel materials both with high oxygen permeability and high structure stability, and this is also my thesis’s purpose.
Based on the previous work, the present study was to exploited new mixed-conducting perovksite-type membrane materials for oxygen permeation with the aids of XRD, SEM-EDX, TG-DSC, O2-TPD and H2-TPR analysis.
It was found that it was difficult to synthesize the pure phase BaCo0.4Fe0.4Zr0.2O3-δsince the Zr4+ ion is relatively large for the occupation of the B-site of the perovskite structure, therefore Zn which exhibits constant state was chosen to substitute Zr in BaCo0.4Fe0.4Zr0.2O3-δperovskite, From the XRD analysis, it is proved that the doping of B site of the perovskite structure with a divalent metal like zinc leads to the elimination of nonstoichiometric oxygen variations and lattice expansion of oxygen,from the O2-TPD it can be seen that BaCo0.4Fe0.4Zn0.2O3-δperovskite keep very good structure stability under high temperature and low oxygen partial pressure. Oxygen permeation test was investigated by the gas chromatography, an oxygen permeation flux of 0.9 ml/min.cm2 (6.72×10-7 mol/cm2.s) was found at 950 ?C with a membrane thickness of 0.56 mm. It was also found out that the oxygen permeation was controlled by the bulk diffusion under the experimental conditions. The membrane was steadily operated for more than 100 h in the oxygen permeation test. The XRD analysis after long term test proved that membrane still kept perovskite structure without been destroyed.
The effects of Ta ion doping on the structure,high temperature oxygen desorption(O2-TPD), high temperature hydrogen reduction and oxygen transporting properties of SrCo(1-y)TayO3-δ(y=0.0, 0.01, 0.05, 0.1, 0.2, 0.3)were investigated. The perovskite phase structure of the as prepared SrCo(1-y)TayO3-δwas shown to change in the sequence of the hexagonal– cubic– cubic + browmnillerite as Ta ion content y increased. It was found that SrCo0.9Ta0.1O3-δpossessed the most optimized perovskite phase structure. The SrCo0.9Ta0.1O3-δmembrane was investigated by SEM-EDX analysis, it was found that membrane was dense and the compositions both on the surface and the cross agreed with SrCo0.9Ta0.1O3-δstoichiometry. Oxygen permeation test was performed within the temperature range of 700 - 950 oC, and the oxygen permeation flux of 2.07 ml/min·cm2 (1.63×10-6 mol/cm2.s)was obtained at 950°C with a thickness of 0.65 mm. It was found that the oxygen permeation of SrCo0.9Ta0.1O3-δmembrane disk were controlled by the bulk diffusion under the research conditions. The oxygen permeation fluxes varied within a very narrow range, i.e., from 1.70 to 1.96 ml/min·cm2 in the entire 520 h long-term operation. The XRD analysis of the spent membrane showed that the perovskite structure had been well preserved after the long-term permeation test both in the air feed gas side and He sweep gas side which indicated that SrCo0.9Ta0.1O3-δceramic membrane was a promising material used in high-temperature oxygen separation.
引文
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