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Membrane duale de reformage et de filtration pour la production d'hydrogène par réaction de craquage de méthane

机译:甲烷裂化反应生产氢气的双重重整和过滤膜

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摘要

In a context of rarefaction and increasing of prices of fossil energetic resources, it is necessary to diversify the energetic offer. Hydrogen seems to be one of the most promising vectors, although technological matters associated to its production slow down its development. In this context, the present work aims at elaborating a system able to produce pure hydrogen from hydrocarbon, and in particularly from methane. It is constituted of three membranes, which specific roles are reforming, separation and restitution of molecular hydrogen. The first membrane is porous and is made of a cermet BaCe0.85Y0.15O3-a / nickel. The second one is dense and is elaborated either simply from BaCe0.85Y0.15O3-a, or from the same cermet as the first membrane, depending whether the system operates in a galvanic or in a non-galvanic mode. The last one is of the same nature and morphology as the first one. The three membranes are fabricated and coupled one with the others by the process called co-tape-casting in organic solvent followed by a step of co-sintering. More precisely, on the free surface of the first membrane a layer of a mixture of powders Xj / Ni, where Xj and Ni are respectively the support and the catalyst for methane cracking reaction (Xj = CeO2, Silica, Nanodiamonds, zeolithes,...), is deposited via a humid route. Then, by feeding with methane this system, with for example the presence of the highly efficient couple CeO2/Ni, the production of hydrogen is made possible and deposited carbon atoms form nanotubes with Ni particles at their tops, which are then always in the methane flux, and which then do not suffer from deactivation. Hydrogen enters then in the porosity of the first membrane where it is oxidized when meeting with triple phases boundaries. In a non-galvanic system, protons and electrons can go through the second membrane, following the percolating proton and ion conducting paths, to reach the third membrane. In a galvanic system, electrons are transported toward the third membrane via an external circuit, which imposes a voltage. At the third membrane triple phase boundaries, electrons and protons recombine to form pure molecular hydrogen. These two systems galvanic and non galvanic have been designed and fabricated, and the motivation that has led to the choice of the materials used was given at each step of the process. Thanks to the comprehension of the different phenomena taking place during operating conditions, a rather optimized process leading to a system of production and purification of hydrogen was realized. Finally, a numeric model was developed, in order to tailor the influence of all the different parameters that may influence the performances of the object.
机译:在稀缺化石和能源资源价格上涨的背景下,有必要使能源资源多样化。氢似乎是最有前途的媒介之一,尽管与其生产相关的技术问题减缓了其发展。在这种情况下,本发明的目的是设计一种能够从烃类,特别是从甲烷中产生纯氢的系统。它由三个膜组成,其具体作用是分子氢的重整,分离和复原。第一膜是多孔的,并且由金属陶瓷BaCe0.85Y0.15O3-a /镍制成。第二个是致密的,可以简单地由BaCe0.85Y0.15O3-a制成,也可以由与第一个膜相同的金属陶瓷制成,具体取决于系统是在电流模式下还是在非电流模式下运行。最后一个与第一个具有相同的性质和形态。通过在有机溶剂中进行共胶带浇铸的过程,然后进行共烧结步骤,制造了三种膜并将它们彼此耦合。更准确地说,在第一膜的自由表面上,一层粉末Xj / Ni的混合物,其中Xj和Ni分别是甲烷裂解反应的载体和催化剂(Xj = CeO2,二氧化硅,纳米金刚石,沸石等)。 。),通过潮湿的路径沉积。然后,通过向该系统供入甲烷,例如在存在高效的一对CeO2 / Ni的情况下,就可以产生氢,并且沉积的碳原子形成纳米管,其顶部具有Ni颗粒,这些颗粒始终位于甲烷中助焊剂,然后便不会失活。氢然后进入第一膜的孔隙中,在遇到三相边界时被氧化。在非电系统中,质子和电子可以沿着渗透的质子和离子传导路径穿过第二层膜,到达第三层膜。在电流系统中,电子通过施加电压的外部电路向第三膜传输。在第三膜三相边界处,电子和质子复合形成纯分子氢。已经设计并制造了这两种系统,分别是原电池和非原电池,并且在该过程的每个步骤中都给出了导致选择所用材料的动机。由于理解了在运行条件下发生的不同现象,因此实现了相当优化的过程,从而导致了氢气的生产和纯化系统。最后,开发了一个数值模型,以调整可能影响对象性能的所有不同参数的影响。

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  • 作者

    Hafsaoui Julien;

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  • 年度 2009
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  • 原文格式 PDF
  • 正文语种 fr
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