【作者】 周晓艳；

【导师】 周迎春；

【作者基本信息】 辽宁工学院 ， 材料物理与化学， 2007， 硕士

【摘要】 合成气是一种洁净的能源,如何能有效地制备以及合理利用合成气成为近年来研究的热点。CO₂-O₂联合重整CH₄反应是制备合成气的有效途径之一。它以CH₄和CO₂这两种具有温室效应的气体为原料制备合成气,对环境保护具有积极的意义,而且随着工业上对合成气的需求日益增长,该联合重整反应也具有良好的工业前景,因此吸引了众多研究者的目光。目前制约CO₂-O₂联合重整CH₄反应工业化的主要原因之一就是反应中催化剂的积炭失活问题。本论文对CO₂-O₂联合重整CH₄制合成气反应用镍基催化剂进行了研究。首先以Zr、Ce无机盐为前体制备复合氧化物载体。讨论了制备方法、焙烧方式等因素对载体性质的影响。然后采用浸渍法制备负载型Ni催化剂Ni/ZrO₂-CeO₂,考察了不同溶剂浸渍活性组分及载体Ce/Zr比例对催化剂性质的影响。通过常压固定床反应器对催化剂进行活性评价与筛选。最后利用BET、XRD等技术手段对载体和催化剂进行表征,将表征结果与反应性能相关连,得出适宜联合重整进行的催化剂及工艺条件。当载体Ce/Zr为1/2,采用流动氮气-静态空气（FN2-SAir）焙烧3h时比表面积最大,其负载Ni的含量为9wt%的催化剂活性最佳。联合重整工艺条件为催化剂还原温度850℃,反应温度850℃,W/F=0.5×10-4g·（ml·h-1）-1,原料气配比为CH₄:CO₂:O₂=4:2:1（体积比）时,以9%Ni/ZrO₂-CeO₂（Ce/Zr=1/2）为催化剂进行重整反应,CH₄和CO₂的初始转化率分别可以达到95.1%和95.3%,反应进行120h后催化剂仍保持较高的催化活性,说明该催化剂的活性和稳定性均较好,具有良好的工业应用前景。更多还原

【Abstract】 There is considerable interesting in the efficient producing and feasible use of syngas as a clean energy source recently. Reforming of methane with CO₂-O₂ is one of the most promising methods to produce syngas. It takes two kinds of green house gases, CH₄ and CO₂, as the raw material to produce syngas, and is beneficial for environment protection. With the increasing demand of syngas, reforming of methane with CO₂-O₂ shows a promising industrial future, and attracts more and more attentions of researchers. The main obstacle in industrialization of methane reforming is the deactivation of the employed catalyst due to carbon deposition.In this work, reforming of methane with CO₂-O₂ was studied using Ni-based catalysts. Inorganic salts of Ce/Zr were used as the precursor to prepare oxide complex supports. The influences of preparation and calcinations methods on the supports properties were discussed. Ni/ZrO₂-CeO₂ was prepared by impregnation methods. The effect of solvent and Ce/Zr ratio were investigated. The activity measurements were carried out on fixed bed reactor under ambient pressure. The supports and catalysts were characterized by BET, XRD. The optimal catalyst and reaction conditions for reforming of methane with CO₂-O₂ were obtained by relating the characterization results of carriers/catalysts with their reaction properties.The supports calcined under FN2-SAir for 3 hours with Ce/Zr=1/2 have large specific surface area. The catalysts performed well in the reforming reaction when 9wt% Ni was loaded on them. The initial conversions of CH₄ at 95.1 %and CO₂ at 95.3% were obtained under the reaction condition of reaction temperature and catalyst reduction temperature at 850℃, with W/F of 0.5×10-4g·（ml·h-1）-1 and a raw material volume ratio of CH₄:CO₂:O₂=4:2:1, take 9% Ni/ZrO₂-CeO₂ （Ce/Zr=1/2） as the catalysts. And the conversationswere kept constant during experimental 120 hours, which indicating that the catalysts were excellent in activity and stability. The catalysts prepared by this method, therefore, showed a promising perspective for industrial applications.更多还原