一种钯膜组件透氢性能的实验研究
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摘要
氢能,被视为本世纪最具发展潜力的清洁能源,它能代替石油化工等传统化石能源,从而也被视为解决温室效应问题,提高能量利用率的有效替代二次能源。目前世界上绝大部分的氢气生产主要是采用天然气重整以及部分氧化反应,其主要的分离方法是变压吸附。在氢气生产过程中,氢气分离成本占相当大的一部分,钯膜因其独特的氢气选择透过性能引起了人们的关注,它可以分离得到高纯度的氢气,同时它还可以与氢气的生产过程相耦合。目前对钯膜制备方法、钯膜性能以及钯膜反应器都有一些详细的研究,对于大多数钯膜性能的研究主要集中在单纯的钯膜以及钯合金膜,对于钯膜组件性能的研究还比较少,本文就一种新型的钯膜组件性能进行了详细的研究。
钯膜组件主要包括:Pd-Ag合金膜、多孔烧结金属材料、不锈钢框架以及盲板法兰,利用一个可控制温度的压力容器内测试了钯膜组件的性能。利用电子扫描电镜对钯膜组件的表面以及测试之后的多孔烧结金属材料表面进行表征。研究钯膜组件的即时氢气透过量,操作条件对钯膜组件的影响。在研究操作条件对钯膜组件氢气透过量以及透过效率的影响中发现,钯膜组件的氢气透过量随着温度的升高而增加,随着高压侧氢气压强的升高而增加,随着低压侧氢气分压的减小而增加。钯膜组件的氢气透过效率随着温度的升高而减小,随着高压侧氢气分压的升高而增加,随着低压侧氢气分压的减小而减小。减小Pd-Ag合金膜的厚度有利于提高钯膜组件的氢气透过量。在钯膜组件即时氢气透过性能的研究中发现, 0.2μm规格多孔烧结金属材料不适合在温度高于755 K的环境下作为钯膜组件的支撑体,通过电子扫描电镜观察多孔烧结金属的表面发现在高温高压的环境下,0.2μm规格的多孔烧结金属材料的表面结构发生了变化,导致钯膜组件的氢气透过性能减小。0.5μm规格多孔烧结金属材料在869 K-943 K的范围内仍然可以保持较好的氢气透过性能。多孔烧结金属材料的前期处理有助于增加钯膜表面的光滑度,但是同时也减小了钯膜组件对氢气的选择性透过能力。利用Sieverts’Law描述钯膜组件氢气透过量时需要进行校正,其校正系数η的取值根据实验条件的不同而不同。
The increased demand for pure hydrogen gas in recent years in many sectors, rangingfrom petroleum processing, materials treatment to renewable energy related applications, hasled to a revival of interest in economical hydrogen production technologies. Hydrogen energyis looked upon as a savior in combating the deterioration of the global environment, as meansof securing energythat is independent of the dwindling fossil fuel supplyand an approach to afuture lasting supply of energy resource. Most of the world's hydrogen is generated by steamreforming or partial oxidation of natural gas in parallel fixed bed reactors within hugetop-fired or side-fired furnaces, coupled with pressure swing adsorption (PSA) for hydrogenpurification. Hydrogen separation accounts for a large fraction of energy expenditure andcapital investment in the hydrogen production process. The most widely used technology forhydrogen purification is PSA. Palladium and its alloy membranes have attracted growinginterests for their capability to separate ultra-pure hydrogen from gaseous mixtures. They canalso be integrated with chemical reactors where chemical reaction and hydrogen separationoccur simultaneously to simplify the hydrogen production process. Various membranefabricated methods, performance and membrane reactors have been researched. This paperwas comprehensivelyinvestigated a new palladium membrane module performance.
Membrane modules, consisting of membrane foil, porous stainless steel substrate, testframe and flange were assembled and tested in an electrically heated vessel. Instantaneoushydrogen permeation flux was measured. Influences of operation conditions on membraneperformance were examined. Microstructure and morphology of the membrane surfaces werecharacterized by scanning electron microscopy. For the conditions investigated, permeationfluxes of the membrane module increased with increasing the hydrogen pressure in the vesselside and increasing the membrane module temperature and decreasing the hydrogen exitpartial pressure by sweep gas. The permeation fluxes increased with decreasing membranethickness. However, the thickness was less than 10μm was not suitable for fabricated on the porous stainless steel. The permeation factor of the module increases with increasing thehydrogen pressure in the vessel side and decreasing the membrane module temperature. Withdecreasing the hydrogen exit partial pressure by sweep gas, the membrane module permeationflux increased, while the permeation factor decreased. It was observed that for operationtemperature higher than 755 K, 0.2?m grade porous 316L stainless steel material was notsuitable for being used as membrane module substrate and the surface of porous stainless steelwas changed. For temperature around 869 K -943 K, 0.5 ?m grade porous 316Lstainless steel material without any pretreatment can be used as membrane module substrate. Pretreatmentof the 0.5 ?m grade substrate helped to smooth membrane foil surface. However, it changedthe surface structure of the material and led to permeabilitydecrease.
钯膜组件主要包括:Pd-Ag合金膜、多孔烧结金属材料、不锈钢框架以及盲板法兰,利用一个可控制温度的压力容器内测试了钯膜组件的性能。利用电子扫描电镜对钯膜组件的表面以及测试之后的多孔烧结金属材料表面进行表征。研究钯膜组件的即时氢气透过量,操作条件对钯膜组件的影响。在研究操作条件对钯膜组件氢气透过量以及透过效率的影响中发现,钯膜组件的氢气透过量随着温度的升高而增加,随着高压侧氢气压强的升高而增加,随着低压侧氢气分压的减小而增加。钯膜组件的氢气透过效率随着温度的升高而减小,随着高压侧氢气分压的升高而增加,随着低压侧氢气分压的减小而减小。减小Pd-Ag合金膜的厚度有利于提高钯膜组件的氢气透过量。在钯膜组件即时氢气透过性能的研究中发现, 0.2μm规格多孔烧结金属材料不适合在温度高于755 K的环境下作为钯膜组件的支撑体,通过电子扫描电镜观察多孔烧结金属的表面发现在高温高压的环境下,0.2μm规格的多孔烧结金属材料的表面结构发生了变化,导致钯膜组件的氢气透过性能减小。0.5μm规格多孔烧结金属材料在869 K-943 K的范围内仍然可以保持较好的氢气透过性能。多孔烧结金属材料的前期处理有助于增加钯膜表面的光滑度,但是同时也减小了钯膜组件对氢气的选择性透过能力。利用Sieverts’Law描述钯膜组件氢气透过量时需要进行校正,其校正系数η的取值根据实验条件的不同而不同。
The increased demand for pure hydrogen gas in recent years in many sectors, rangingfrom petroleum processing, materials treatment to renewable energy related applications, hasled to a revival of interest in economical hydrogen production technologies. Hydrogen energyis looked upon as a savior in combating the deterioration of the global environment, as meansof securing energythat is independent of the dwindling fossil fuel supplyand an approach to afuture lasting supply of energy resource. Most of the world's hydrogen is generated by steamreforming or partial oxidation of natural gas in parallel fixed bed reactors within hugetop-fired or side-fired furnaces, coupled with pressure swing adsorption (PSA) for hydrogenpurification. Hydrogen separation accounts for a large fraction of energy expenditure andcapital investment in the hydrogen production process. The most widely used technology forhydrogen purification is PSA. Palladium and its alloy membranes have attracted growinginterests for their capability to separate ultra-pure hydrogen from gaseous mixtures. They canalso be integrated with chemical reactors where chemical reaction and hydrogen separationoccur simultaneously to simplify the hydrogen production process. Various membranefabricated methods, performance and membrane reactors have been researched. This paperwas comprehensivelyinvestigated a new palladium membrane module performance.
Membrane modules, consisting of membrane foil, porous stainless steel substrate, testframe and flange were assembled and tested in an electrically heated vessel. Instantaneoushydrogen permeation flux was measured. Influences of operation conditions on membraneperformance were examined. Microstructure and morphology of the membrane surfaces werecharacterized by scanning electron microscopy. For the conditions investigated, permeationfluxes of the membrane module increased with increasing the hydrogen pressure in the vesselside and increasing the membrane module temperature and decreasing the hydrogen exitpartial pressure by sweep gas. The permeation fluxes increased with decreasing membranethickness. However, the thickness was less than 10μm was not suitable for fabricated on the porous stainless steel. The permeation factor of the module increases with increasing thehydrogen pressure in the vessel side and decreasing the membrane module temperature. Withdecreasing the hydrogen exit partial pressure by sweep gas, the membrane module permeationflux increased, while the permeation factor decreased. It was observed that for operationtemperature higher than 755 K, 0.2?m grade porous 316L stainless steel material was notsuitable for being used as membrane module substrate and the surface of porous stainless steelwas changed. For temperature around 869 K -943 K, 0.5 ?m grade porous 316Lstainless steel material without any pretreatment can be used as membrane module substrate. Pretreatmentof the 0.5 ?m grade substrate helped to smooth membrane foil surface. However, it changedthe surface structure of the material and led to permeabilitydecrease.
引文
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