La交换NaY分子筛中的离子定位和迁移规律

doi:10.1016/S1872-2067(11)60622-6

催化学报 ›› 2013, Vol. 34 ›› Issue (8): 1599-1607.DOI: 10.1016/S1872-2067(11)60622-6

La交换NaY分子筛中的离子定位和迁移规律

杜晓辉^a,b, 张海涛^b, 李雪礼^b, 谭争国^b, 刘宏海^b, 高雄厚^b

a 西北师范大学化学化工学院, 甘肃兰州730070;
b 中国石油石油化工研究院兰州化工研究中心, 甘肃兰州730060

收稿日期:2013-04-13 修回日期:2013-05-14 出版日期:2013-08-16 发布日期:2013-07-30
通讯作者: 高雄厚
基金资助:
国家重点基础研究发展计划(973计划, 2010CB226904).

Cation location and migration in lanthanum-exchanged NaY zeolite

Xiaohui Du^a,b, Haitao Zhang^b, Xueli Li^b, Zhengguo Tan^b, Honghai Liu^b, Xionghou Gao^b

a College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, Gansu, China;
b Lanzhou Petrochemical Research Center, Petrochemical Research Institute, PetroChina, Lanzhou 730060, Gansu, China

Received:2013-04-13 Revised:2013-05-14 Online:2013-08-16 Published:2013-07-30
Supported by:
This work was supported by the National Basic Research Program of China (973 Program, 2010CB226904).

摘要/Abstract

摘要： 以NaY分子筛为原料,采用二次交换二次焙烧工艺,制得了LaNH₄Y-1,LaY-1,LaNH₄Y-2和LaY-2四种分子筛样品.采用粉末X射线衍射结合Rietveld结构精修确定了La离子在分子筛中的分布.结果表明,在离子交换过程中,La离子首先定位于分子筛超笼里;经焙烧脱水后,La离子迁移到分子筛方钠石笼并定位在SI′位置.T-O-T键角的变化表明,LaNH₄Y-1表现出最大的骨架扭曲性和结构不稳定性.La离子定位在SI′位置与O3配位,增加了T-O3的键长,表明稀土离子不仅通过控制骨架脱铝抑制晶胞收缩,还可能通过影响T-O3键长使晶胞增大.在REY分子筛中,稀土的主要作用是稳定分子筛结构,从而调节其酸性和催化活性.采用红外光谱和NH₃程序升温脱附考察了La离子和NH₄⁺对分子筛酸性的影响,并总结了稀土离子稳定Y型分子筛的机理.

关键词: LaY型分子筛, Rietveld结构精修, 镧离子迁移, 骨架结构, 热稳定性

Abstract: LaNH₄Y and LaY zeolites were prepared using a double-exchange double-calcination method by La exchange of NaY zeolite. The distribution of the La cations was determined by powder X-ray diffraction with Rietveld refinement. The results indicate that the La cations are initially located in supercages, and then their hydration shells are stripped off and they migrate to small sodalite structures located at SI′ during heating and dehydration. The changes in the T-O-T angles show significant distortion of the flexible framework and instability in LaNH₄Y obtained using a one-exchange one-calcination process. For La cations located at SI′ and coordinated with O3, the T-O3 bond distance increased, which indicates that the rare-earth cations not only restrain framework dealumination, suppressing condensation of the unit cell, but also have an effect on the T-O3 bond distance, increasing the unit cell volume. The role of the rare-earth species is to ensure the hydrothermal stability of the zeolite in order to control the acid site density and catalytic activity. The effects of La cations and NH₄⁺ cations on the zeolite acidity were studied using infrared spectroscopy and NH₃ temperature-programmed desorption, and the mechanism of rare-earth stabilization of the Y zeolite is described.

Key words: LaY zeolite, Rietveld refinement, Lanthanum cation migration, Framework structure, Thermal stability

杜晓辉, 张海涛, 李雪礼, 谭争国, 刘宏海, 高雄厚. La交换NaY分子筛中的离子定位和迁移规律[J]. 催化学报, 2013, 34(8): 1599-1607.

Xiaohui Du, Haitao Zhang, Xueli Li, Zhengguo Tan, Honghai Liu, Xionghou Gao. Cation location and migration in lanthanum-exchanged NaY zeolite[J]. Chinese Journal of Catalysis, 2013, 34(8): 1599-1607.

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La交换NaY分子筛中的离子定位和迁移规律

Cation location and migration in lanthanum-exchanged NaY zeolite

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