载体酸性对Mo/HZSM-5-Al_2O_3催化剂上烯烃歧化反应性能的影响  

Effects of Support Acidity on the Catalytic Performance of Mo/HZSM-5-Al_2O_3 Catalysts in Olefin Metathesis

作　　者：张大洲[1,2] 李秀杰[1] 刘盛林[1] 朱向学[1] 辛文杰[1] 谢素娟[1] 曾蓬[3] 徐龙伢[1] 

机构地区：[1]中国科学院大连化学物理研究所,辽宁大连116023 [2]中国科学院研究生院,北京100049 [3]中国寰球工程公司辽宁分公司,辽宁抚顺113006

出　　处：《催化学报》2011年第11期1747-1754,共8页

基　　金：国家自然科学基金(20903088)~~

摘　　要：在固定床反应器上考察了Mo/HZSM-5-Al2O3催化剂上乙烯与2-丁烯歧化制丙烯反应的性能.结合X射线衍射、NH3程序升温脱附、吡啶吸附红外光谱、H2程序升温还原和程序升温氧化等表征结果发现,载体酸性的差异导致催化剂酸性和Mo物种落位方式不同.载体酸性较强时,催化剂积炭严重,反应稳定性差;载体酸性较弱时,Mo物种在分子筛孔道内以(Mo2O5)2+团簇形式存在,而在Al2O3表面形成较多易还原的六配位Mo物种,催化活性低,并呈现出一定的诱导期;适中酸性的载体有利于Mo物种的分散和活化,表现出了最佳的歧化反应活性.Mo/HZSM-5-Al2O3 catalyst samples, where the HZSM-5 had different Si/Al ratios （12, 42, and 213）, were prepared and evaluated in a fixed-bed reactor. Effects of support acidity changes on the catalytic performance of Mo/HZSM-5-Al2O3 in the metathesis of ethene and 2-butene to propene were investigated. NH3 temperature-programmed desorption and pyridine infrared spectra revealed that the differences in support acidity led to the different anchoring modes of Mo species on the composite supports. Quick deactivation phenomena were observed on Mo/HZSM-5-Al2O3 （Si/Al = 12） due to the high acidity density of the catalyst. For Mo/HZSM-5-Al2O3 （Si/Al = 213）, more Mo species dispersed on the alumina in octahedral form and those locating in the zeolite channels existed in the state of （Mo2O5）2＋ clusters evidenced by ultraviolet-visible diffuse reflectance spectroscopy and H2 temperature-programmed reduction results. Such distribution was linked with the low metathesis activity and the appearance of the induction period on Mo/HZSM-5-Al2O3 （Si/Al = 213）. Mo/HZSM-5-Al2O3 （Si/Al = 42） sample demonstrated the best catalytic activity and reaction stability among the three samples. This was attributed to its suitable acidity amount and optimal distribution of Mo species on the support.

关 键 词：乙烯 丁烯 歧化反应 丙烯 载体酸性 HZSM-5分子筛 氧化铝 

分 类 号：O643.32[理学—物理化学]