多级孔NiMo负载TS-1分子筛催化剂的制备及其加氢脱硫性能
Hierarchical TS-1 zeolite loaded with NiMo catalysts: Preparation and performance in hydrodesulfurization
作者单位E-mail
周文武 西安科技大学化学与化工学院, 西安 710054
西部煤炭绿色安全开发国家重点实验室(筹), 西安 710054 
 
韩峙宇 西安科技大学化学与化工学院, 西安 710054  
陈治平 西安科技大学化学与化工学院, 西安 710054
西部煤炭绿色安全开发国家重点实验室(筹), 西安 710054 
cupczp@163.com 
段瑛锋 西安科技大学化学与化工学院, 西安 710054
西部煤炭绿色安全开发国家重点实验室(筹), 西安 710054 
 
康洁 西安科技大学化学与化工学院, 西安 710054  
樊飞 西安科技大学化学与化工学院, 西安 710054  
田昌 西安科技大学化学与化工学院, 西安 710054  
张新梦 西安科技大学化学与化工学院, 西安 710054  
摘要: 钛硅(TS-1)分子筛的微孔孔道严重限制了其在复杂分子催化转化中的应用,为了克服这一问题,通过酸洗脱、碱刻蚀及二者相结合的方法制备了多级孔TS-1分子筛,并采用等体积共浸渍法制备了相应的NiMo负载型催化剂;使用X射线衍射(XRD)、N2吸附-脱附、吡啶吸附红外光谱(Py-FTIR)、氢气程序升温还原(H2-TPR)、X射线光电子能谱(XPS)和高分辨透射电子显微镜(HR-TEM)等方法对多级孔TS-1分子筛的理化性质进行了表征;以二苯并噻吩(DBT)为探针对催化剂的加氢脱硫(HDS)性能进行了评价。结果表明,和常规TS-1分子筛相比,多级孔TS-1分子筛保持了MFI拓扑结构,比表面积增大且具有介孔结构,分子筛表面形成了适量的Brønsted酸中心;相应催化剂上活性金属与载体间相互作用得以改善,MoS2片晶长度和堆垛层数适宜,形成了更多的NiMoS活性相;催化剂活性和选择性均有所提升,尤其是酸洗脱获得的NiMo/AT-TS-1催化剂的活性相较未经处理的NiMo/TS-1催化剂提升了1.2倍,直接脱硫(DDS)路径选择性提升了22%。
关键词: 多级孔TS-1分子筛  NiMo负载TS-1催化剂  活性相  二苯并噻吩  加氢脱硫
基金项目: 国家自然科学基金(No.21908174,22178283)和陕西省重点研发计划(No.2020GY-136)资助。
Abstract: The sole micropores strictly restrict the wide utilization of TS-1 zeolite in the catalytic fields, especially in the catalytic conversion of compounds with large molecular sizes. Here, we report a feasible and economical method to overcome this drawback. In this work, the hierarchical TS-1 zeolite was constructed via post-acid treatment, postalkali etching, and a combination of postacid treatment and alkali etching methods, after which, the corresponding NiMo-supported catalysts were prepared via the incipient wetness impregnation method. Then, the aforementioned materials were fully characterized using X-ray diffraction (XRD), N2 adsorption-desorption, pyridine adsorbed Fourier transform infrared spectroscopy (Py-FTIR), H2 temperature programmed reduction (H2-TPR), X-ray photoelectron spectroscopy (XPS), and high-resolution transition electron microscope (HR-TEM) to unravel the changes in the physicochemical properties caused by the post treatments. Finally, the hydrodesulfurization of dibenzothiophene (DBT) was used as a probe to assess the effects of the post-treatments on the catalytic performance of the hierarchical NiMo/TS-1 catalysts. The results showed that the MFI topology of TS-1 zeolite remained undamaged significantly and the serial hierarchical TS-1 zeolites exhibited higher specific surface areas and mesopore structures. Moreover, appropriate amounts of Brønsted acid sites were formed at the surface of the serial hierarchical TS-1 zeolites. The interaction between the active metals and the support materials was also modulated by the posttreatment of TS-1 zeolite, which resulted in better dispersion of Ni promoted MoS2 slabs with a higher proportion of NiMoS active phase, further leading to the enhanced catalytic activity and direct desulfurization pathway selectivity of the corresponding serial hierarchical NiMo/TS-1 catalysts. Among all the prepared catalysts, the catalytic activity was enhanced by approximately 1.2 times over catalyst NiMo/AT-TS-1 obtained by post-acid treatment compared to that over catalyst NiMo/TS-1 without treatment and on which the selectivity of the DDS pathway was 22% higher compared to that over catalyst NiMo/TS-1.
Keywords: hierarchical TS-1 zeolite  TS-1 zeolite loaded with NiMo catalyst  active phase  dibenzothiophene  hydrodesulfurization
投稿时间:2022-12-05 修订日期:2023-03-23
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周文武,韩峙宇,陈治平,段瑛锋,康洁,樊飞,田昌,张新梦.多级孔NiMo负载TS-1分子筛催化剂的制备及其加氢脱硫性能[J].无机化学学报,2023,39(5):891-905.
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