Pan Liuyi, He Yulong, Niu Menglong, Dan Yong, Li Wenhong
School of Chemical Engineering, Northwest University Xi'an Shaanxi 710069 P. R. China
College of Chemistry & Chemical Engineering, Baoji University of Arts and Sciences Baoji 721013 Shaanxi China.
RSC Adv. 2019 Jul 5;9(37):21175-21185. doi: 10.1039/c9ra02791b.
Ni-M/SiO with different binary metals M (M = Ce, Co, Sn, Fe) prepared by an incipient impregnation method was used in the hydrodeoxygenation (HDO) of low-temperature coal tar distillate, which is rich in phenolic compounds. -Cresol, as a model compound of the distillate, was used to evaluate the activity and selectivity of BTX products on the series of reduced Ni-M/SiO catalysts in a fixed bed reactor. The properties of the catalysts were characterized by N adsorption-desorption, ICP-AES, XRD, H-TPR, and XPS. Benzene and toluene as the direct deoxygenation (DDO) products and cyclohexane and methylcyclohexane as the hydrogenolysis (HYD) products were detected to evaluate the selectivity of the path in the deoxygenation process. In this series of catalysts, the order of reactivity was Ni-Ce > Ni-Sn > Ni-Co > Ni-Fe > monometallic Ni. Meanwhile, the addition of Ce and Co loaded in the Lewis acid sites of the catalyst affected the electron distribution of nickel atom and its atomic arrangement on the surface of the carrier. Compared to monometallic Ni, the DDO path become dominant on Ni-Ce and Ni-Co and the selectivity for BTX products increased from 58.8% to 77.4% and 71.1%, respectively. The binary metal Sn, unlike the former two metals, formed a NiSn crystal form with Ni, which resulted in significant enhancement of the HYD path while obviously increasing the reactivity.
采用初湿浸渍法制备的含有不同二元金属M（M = Ce、Co、Sn、Fe）的Ni-M/SiO用于富含酚类化合物的低温煤焦油馏分的加氢脱氧（HDO）反应。以对甲酚作为馏分的模型化合物，在固定床反应器中用于评价一系列还原态Ni-M/SiO催化剂上BTX产物的活性和选择性。通过N2吸附-脱附、ICP-AES、XRD、H-TPR和XPS对催化剂的性能进行了表征。检测了作为直接脱氧（DDO）产物的苯和甲苯以及作为氢解（HYD）产物的环己烷和甲基环己烷，以评价脱氧过程中路径的选择性。在这一系列催化剂中，反应活性顺序为Ni-Ce＞Ni-Sn＞Ni-Co＞Ni-Fe＞单金属Ni。同时，负载在催化剂Lewis酸位点上的Ce和Co的添加影响了镍原子的电子分布及其在载体表面的原子排列。与单金属Ni相比，在Ni-Ce和Ni-Co上DDO路径占主导，BTX产物的选择性分别从58.8%提高到77.4%和71.1%。二元金属Sn与前两种金属不同，它与Ni形成了NiSn晶型，这导致HYD路径显著增强，同时反应活性明显提高。
