富氢气体纯化过程中钯膜的抑制作用与偏析现象研究

氢气作为一种清洁、高效、可持续的能源，在我国能源结构中占据重 要地位。液体甲醇比氢气更易于储运，结合甲醇与水蒸汽在线重整制氢， 可在应用端便捷地使用氢气。通过重整得到的富氢气体中仍含有 CO2、CO 等杂质，需要使用钯膜等分离方法对富氢气体进行纯化。然而，钯膜的纯 化效果会随着纯化温度、气体组分浓度而变化，从而导致钯膜的纯化性能 下降。为进一步阐明钯膜在富氢气体纯化过程中性能下降的机理，分析不 同机理作用的条件和范围，明确钯膜操作适宜的温度边界，本论文针对钯 膜纯化富氢气体过程中的抑制作用和偏析现象，分别开展以下两部分研究： 选取 Pd-Au 合金膜管作为研究对象，以 CO2、CO 作为非渗透气体组分， 通过实验研究非渗透气体组分浓度、纯化温度对钯膜氢渗透过程中抑制作 用的影响。使用 Caravella 模型计算浓差极化作用系数、竞争吸附作用系数、 综合抑制作用系数，以量化并分析各类作用的大小。研究结果表明：三种 抑制作用与非渗透组分浓度均呈正相关。随着纯化温度升高，浓差极化作 用均无明显变化，而 CO2 的竞争吸附作用在高浓度（15%~25%）区减小。 CO2 的综合抑制作用由浓差极化作用主导，CO 的综合抑制作用由竞争吸附 作用主导。相同浓度下，CO 的综合抑制作用强于 CO2。 采用 Pd-Au 合金膜管样品作为研究对象，分析不同气氛、温度下钯膜 的偏析现象。在 H2/N2、H2/CO2、H2/CO、甲醇蒸汽重整气四种气氛下， 400°C~500°C 之间对钯膜样品进行热处理，随后通过 SEM-EDX、XPS、 XRD 分析其偏析前后表面形貌、组成及晶相结构的变化。研究结果表明， 钯膜初始元素组成：85%Pd/15%Au。在四种气氛下，温度大于等于 440°C 时，均在钯膜表面观察到富 Pd 颗粒析出的偏析现象。随温度进一步升高， 富 Pd 颗粒的 Pd 含量升高、尺寸增大、数量增多，偏析程度加剧。在相同 温度下，不同气氛钯膜偏析的程度不同，由强到弱的顺序为 H2/CO、H2/N2、 H2/CO2，推测与气体分子与 Pd 之间的作用力强弱存在关联。为验证偏析对 钯膜渗氢性能的影响，展开 Pd-Au 钯膜管对甲醇蒸汽重整气的纯化实验。 结果显示，440°C 时氢通量降低，表明此温度偏析降低了钯膜渗氢性能。

As a clean, efficient and sustainable energy, hydrogen plays an important role in the energy structure of China. Liquid methanol is easier to store and transport than hydrogen. Combining methanol and steam reforming to produce hydrogen, hydrogen can be easily used in the application end. The hydrogen-rich gas obtained by methanol reforming still contains impurities such as CO2 and CO, so it needs to be purified by separation technology such as palladium membrane. However, the purification efficiency of palladium membrane varies with the purification temperature and concentration of gas components, which leads to the degradation of the purification performance of palladium membrane. In order to further clarify the mechanism of performance degradation of palladium membrane in the purification of hydrogen-rich gas, analyze the conditions and scope of different mechanisms, and clarify the appropriate temperature operation boundary of palladium membrane, this thesis conducted two studies respectively on the inhibition and segregation phenomenon of palladium membrane in the purification of hydrogen-rich gas. Pd-Au alloy tube was selected as the research object, and CO2 and CO were used as non-permeable gas components. The effects of non-permeable gas component concentration and purification temperature on the inhibition of hydrogen penetration of palladium film were studied experimentally. Car avella model was used to calculate the concentration polarization coefficient, competitive adsorption coefficient and comprehensive inhibition coefficient to quantify and analyze the magnitude of various effects. The results showed that the three kinds of inhibition effects were positively correlated with the concentration of non-permeable components. With the increase of purification temperature, concentration polarization effect did not change significantly, while the competitive adsorption effect of CO2 decreased in the high concentration (15%-25%) region. The comprehensive inhibition effect of CO2 was dominated by concentration polarization effect, and the comprehensive inhibition effect of CO was dominated by competitive adsorption effect. At the same concentration,the comprehensive inhibition effect of CO was stronger than that of CO2. Pd-Au alloy tube samples were used as the research object to analyze the segregation phenomenon of Pd membrane under different atmosphere and temperature. Palladium membrane samples were heat treated at 400°C~500°C in H2/N2, H2/CO2, H2/CO and methanol steam reformate. The surface morphology, surface composition and crystal phase structure of palladium film samples were analyzed by SEM-EDX, XPS and XRD. The results showed that initial element composition of Pd membrane is 85%Pd/15%Au. The segregation of Pd-rich particles was observed on the surface of Pd membrane at temperatures greater than or equal to 440°C in four different atmospheres. With the increase of temperature, the Pd content, size and quantity of Pd-rich particles increase, and the degree of segregation intensifies. At the same temperature, the segregation degree of Pd membrane in different atmospheres is different, and the order from strong to weak is H2/CO, H2/N2, H2/CO2, which is speculated to be related to the strength of the interaction between Pd and gas molecules. In order to verify the effect of segregation on the hydrogenation performance of palladium membrane, the purification experiment of Pd-Au palladium membrane tube on methanol steam reformate was carried out. The results show that the hydrogen flux of palladium membrane decreased at 440°C, indicating that segregation reduced the hydrogen permeability of palladium film at this temperature.

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