应用于C9石油树脂催化加氢的高性能Ni2P/SiO2催化剂研究

催化加氢是提高C9石油树脂产品质量的有效手段。本文采用程序升温还原法(TPR法)制备了Ni2P/SiO2催化剂并应用于C9石油树脂加氢反应中，考察了温度、压力、液时空速的影响。结果表明，该体系的最佳反应条件分别为：250℃, 6 MPa, 和1 h-1。其中，加氢产物可以在300小时内保持较低溴值(~250 mgBr/100g)，表明Ni2P/SiO2催化剂具有高活性和稳定性。随后，采用XRD、BET、SEM、TEM和红外—吡啶吸附等手段对反应前后催化剂进行表征，以考察其高活性和稳定性的原因。结果表明，相比于NiWS的层状结构，Ni2P是类球形结构，使其暴露出更多的活性位，这可能是Ni2P具有高活性的原因。Ni2P/SiO2催化剂具有高稳定性可能由于Ni2P具有抗硫、抗烧结、抗结焦和抗积碳的性能，这些性能又进一步归因于Ni2P在含硫杂质下可能形成Ni-P-S晶相，Ni2P纳米颗粒具有高热稳定性以及Ni2P催化剂表面弱酸性。

Highly Active and Stable Ni2P/SiO2 Catalyst for the Hydrogenation of C9 Petroleum Resin

Catalytic hydrogenation is an applicable method for the improvement of C9 petroleum resin (C9PR) quality. In this study, the Ni2P/SiO2 catalyst prepared by temperature-programmed reduction (TPR) method was used for hydrogenation of C9 petroleum resin. The effect of reaction conditions on performance was studied, and the results showed that the optimum reaction temperature, pressure and liquid hourly space velocity (LHSV) were 250℃, 6.0 MPa, and 1.0 h-1, respectively. The Bromine Numbers of hydrogenated products were maintained at low values (~250 mgBr/100g) within 300 h, showing the high activity and stability of Ni2P/SiO2 catalyst. The fresh and spent catalysts were characterized by X-ray diffraction (XRD), BET surface area (BET), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Fourier transform infrared (FTIR) pyridine adsorption. Compared with the traditional sulfurated-NiW catalysts, Ni2P possessed globe-like structure instead of layered structure like NiWS active phase, thereof exposing more active sites, which was responsible for the high activity of Ni2P/SiO2. The stability of Ni2P/SiO2 catalyst was probably due to its high sulfur tolerance, anti-sintering, anti-coking and carbon-resistance abilities. These properties might be further ascribed to the special Ni-P-S surface phase, high thermal stability of Ni2P nanoparticles and weak surface acidity for the Ni2P/SiO2 catalyst.