Alessandro Contini, Martin Jendrlin, Aqeel Al-Ani, Vladimir Zholobenko
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引用次数: 0
摘要
摘要 制备了一系列改性 MAZ 和 LTL 沸石,并用一系列碱金属阳离子进行离子交换。研究表明,钾、铷和铯可以很容易地引入 MAZ 结构中,每个单元格可离子交换约 2 个阳离子。相比之下,在类似条件下,每个单位晶胞中引入的 Li 或 Na 阳离子不足一个。为了更好地了解离子交换沸石的结构和酸性特性,我们使用傅立叶变换红外光谱、X 射线粉末衍射、扫描电子显微镜、X 射线荧光和 N2 物理吸附对其进行了表征。傅立叶变换红外数据表明,马兹石中的桥接羟基具有相当大的异质性。使用吡啶作为探针分子在 MAZ 中检测到的布伦斯特酸和路易斯酸位点的浓度低于其化学成分的预期,桥接 OH 基团的相对可及性从 H-MAZ 的 16% 到 K 交换样品的 28% 不等。这与 N2 吸附-解吸数据一致,表明离子交换材料的微孔容积相当小,也与 NH3-TPD 结果一致,表明存在相当大的传输限制。这项研究表明,马兹石的通道结构部分受阻,导致微孔体积减小,酸位点的进入受到限制。
Structural and Acidic Properties of Ion-Exchanged Mazzite
A range of modified MAZ and LTL zeolites have been prepared and ion-exchanged with a series of alkali metal cations. It has been shown that K, Rb and Cs can be readily introduced into the MAZ structure with ~2 cations ion-exchanged per unit cell. In contrast, less than one cation of Li or Na per unit cell has been introduced under similar conditions. Ion-exchanged zeolites have been characterised using Fourier transform infrared spectroscopy, X-ray powder diffraction, scanning electron microscopy, X-ray fluorescence and N2 physisorption in order to gain a better understanding of their structural and acidic properties. The FTIR data indicate considerable heterogeneity of the bridging OH groups in mazzite. The concentration of both Brønsted and Lewis acid sites detected in MAZ using pyridine as a probe molecule is lower than expected from its chemical composition, with the relative accessibility of the bridging OH-groups varying from 16% for H-MAZ to 28% for K-exchanged samples. This is in agreement with the N2 adsorption-desorption data showing a rather low micropore volume for the ion-exchanged materials and with the NH3-TPD results implying considerable transport limitations. This work demonstrates that the channel structure of mazzite is partially blocked resulting in a decreased micropore volume and limited access to the acid sites.
期刊介绍:
Petroleum Chemistry (Neftekhimiya), founded in 1961, offers original papers on and reviews of theoretical and experimental studies concerned with current problems of petroleum chemistry and processing such as chemical composition of crude oils and natural gas liquids; petroleum refining (cracking, hydrocracking, and catalytic reforming); catalysts for petrochemical processes (hydrogenation, isomerization, oxidation, hydroformylation, etc.); activation and catalytic transformation of hydrocarbons and other components of petroleum, natural gas, and other complex organic mixtures; new petrochemicals including lubricants and additives; environmental problems; and information on scientific meetings relevant to these areas.
Petroleum Chemistry publishes articles on these topics from members of the scientific community of the former Soviet Union.