Liuyi Pan,Yulong He,Menglong Niu,Yong Dan,Wenhong Li
Ni–M/SiO2 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. p-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/SiO2 catalysts in a fixed bed reactor. The properties of the catalysts were characterized by N2 adsorption–desorption, ICP-AES, XRD, H2-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 Ni3Sn crystal form with Ni, which resulted in significant enhancement of the HYD path while obviously increasing the reactivity.
Dry methane reforming (DRM) represents a highly promising approach to greenhouse gas conversion (CO 2 and CH 4 ) to valuable byproducts. However, severe carbon deposition and catalyst deactivation inhibit large-scale applications. The work designed new catalysts with a yolk-shell structure using the water-in-oil microemulsion method. The catalysts were composed of a yolk-shell structure, with Ni-M as the active point and silica as the shell. The catalytic performance evaluation indicates that the Ni-M @SiO 2 catalysts show higher CH 4 and CO 2 conversion compared with the Ni@SiO 2 and conventional catalysts at 750 ℃, suggesting the yolk-shell structure and added M species enhance the DRM activity. The XRD, HRTEM, XPS, BET, H 2 -TPR, and CO 2 -TPD analysis confirmed the existence of yolk-shell configuration and evident electronic effect among Ni, M species, and SiO 2 . The long term measurements indicate that the added M species also bring higher carbon deposition tolerance for DRM, where Ni-Ce@SiO 2 and Ni-Zr@SiO 2 exhibit good structural and catalytic stability for DRM over 100 h. Through XRD, TEM, and TGA characterizations of the exhausted catalysts, it is determined that the coke deposition resistance of the catalyst is improved as a result of increased oxygen mobility and enhanced Ni dispersion on the catalytic surface, both of which are enhanced by the added Ce species. The structural analysis of the spent catalysts indicates that the tolerance of carbon deposition is improved by the yolk-shell samples. This study can offer valuable insights for the development of Ni-based catalysts with exceptional carbon deposition capability for DRM.
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