Tailoring Silicoaluminophosphate SAPO-11 Nanocrystal Morphology: Silicon Content as a Switch for Two-Dimensional Growth and Enhanced Catalytic Performance in Isodewaxing of Gas-to-Liquid Waxes

材料科学 化学工程 催化作用 纳米片 透射电子显微镜 溶解 硅 纳米晶 结晶 扫描电子显微镜 产量(工程) 蜡 色散(光学) 纳米技术 双功能 X射线光电子能谱 水热合成 沥青质 双功能催化剂 热液循环 纳米颗粒 扫描透射电子显微镜 比表面积 润滑油 超临界流体 加氢脱氮
作者
Marat Radikovich Agliullin,D. V. Serebrennikov,E. Gerasimov,Yurii V. Larichev,N. A. Filippova,A. R. Zabirov,Artur I. Malunov,Anastasia A. Chemes,A. V. Volik,R. Е. Yakovenko
出处
期刊:ACS applied nano materials [American Chemical Society]
卷期号:9 (6): 2771-2788 被引量:1
标识
DOI:10.1021/acsanm.5c04997
摘要

Traditional silicoaluminophosphate SAPO-11 catalysts for the isodewaxing of gas-to-Liquid (GTL) waxes suffer from severe diffusion constraints within their one-dimensional (1D) channels, reducing their activity and selectivity. While two-dimensional (2D) nanostructures mitigate this issue, their synthesis typically requires expensive and environmentally unfriendly organic structure-directing agents. This work reports a hydrothermal synthesis of 2D SAPO-11 nanosheets without organic additives, utilizing control over the SiO2 source dispersion and the SiO2/Al2O3 molar ratio. The materials were comprehensively characterized (X-ray fluorescence analysis, powder X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscope, 29Si magic-angle spinning nuclear magnetic resonance spectroscopy, nitrogen adsorption–desorption, X-ray photoelectron spectroscopy, ammonia temperature-programmed desorption), and the 0.5% Pt/SAPO-11 bifunctional catalysts were evaluated in the hydroisomerization of n-hexadecane and real GTL wax derived from CO2. It was established that an ultradispersed SiO2 sol (∼1 nm) at an SiO2/Al2O3 ratio of 0.3 acts as a morphological ″switch″, directing the crystallization toward 2D nanosheets (10–20 nm thick) instead of conventional 3D prisms (∼80 nm). TEM-SAED analysis confirmed that the 1D channels are aligned perpendicular to the nanosheet basal plane, resulting in an ultrashort diffusion path length (∼15 nm). Kinetic studies indicated that this morphology control is achieved through the high dissolution rate of the SiO2 (1 nm) particles, which suppresses three-dimensional crystal growth. The optimized 2D catalyst, Pt/SAPO-11-(1 nm)-0.3, exhibited a high yield of iso-C16 hydrocarbons (>89%). In the isodewaxing of GTL wax, this catalyst afforded a high lubricant base oil yield (69%) with excellent low-temperature fluidity (pour point = −32 °C) at a process temperature 20 °C lower than that required for a microcrystalline counterpart. This study demonstrates an efficient nanoengineering strategy for designing highly selective SAPO-11 catalysts for the sustainable upgrading of GTL feedstocks.
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