MOE Engineering Center of Forestry Biomass Materials and Bioenergy, Beijing Forestry University, Beijing 100083, China.
MOE Engineering Center of Forestry Biomass Materials and Bioenergy, Beijing Forestry University, Beijing 100083, China; Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University, Beijing 100083, China.
Bioresour Technol. 2024 Dec;413:131478. doi: 10.1016/j.biortech.2024.131478. Epub 2024 Sep 10.
Upgrading lignin-oil into advanced fuels or chemicals has been widely studied in recent years. To understand the effect of support type and acidity on the hydrodeoxygenation (HDO) of guaiacol (lignin-oil model compound), Ni-based catalysts were prepared with SiO, AlO and ZSM-5 as supports, respectively. The catalysts were characterized by X-ray diffraction (XRD), N adsorption desorption, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and Pyridine adsorption Fourier-transform infrared (Py-IR). The research results indicate that selective regulation of guaiacol hydrogenation products can be achieved by changing the type and acidity of support. Cyclohexanol is the main product over Ni/SiO, while cyclohexane is the main product over Ni/ZSM-5 series catalysts. Moreover, as the Si/Al ratio increases, the catalytic activity of Ni/ZSM-5 slightly decreases, and the yield of cyclohexane also decreases. The Brønsted acidity of the support is the key to promoting the conversion of cyclohexanol to cyclohexane. The formation of NiAlO is the main reason for the relatively low activity of Ni/AlO. The conversion of guaiacol is as high as 99.2 %, and the yield of cyclohexane is as high as 86.6 % over Ni/ZSM-5(Si/Al = 27). In addition, complete conversion of guaiacol and 92.6 % yield of cyclohexanol were achieved over Ni/SiO. More importantly, Ni/SiO and Ni/ZSM-5(27) are suitable for aromatic substrates with different substituents, respectively.
近年来，将木质素油升级为先进燃料或化学品的研究受到广泛关注。为了研究载体类型和酸度对愈创木酚（木质素油模型化合物）加氢脱氧（HDO）的影响，分别采用 SiO、AlO 和 ZSM-5 作为载体，制备了 Ni 基催化剂。通过 X 射线衍射（XRD）、N 吸附脱附、X 射线光电子能谱（XPS）、透射电子显微镜（TEM）和吡啶吸附傅里叶变换红外光谱（Py-IR）对催化剂进行了表征。研究结果表明，通过改变载体的类型和酸度，可以实现对愈创木酚加氢产物的选择性调控。Ni/SiO 上的主要产物是环己醇，而 Ni/ZSM-5 系列催化剂上的主要产物是环己烷。此外，随着 Si/Al 比的增加，Ni/ZSM-5 的催化活性略有降低，环己烷的产率也降低。载体的 Brønsted 酸度是促进环己醇转化为环己烷的关键。NiAlO 的形成是 Ni/AlO 活性相对较低的主要原因。在 Ni/ZSM-5（Si/Al=27）上，愈创木酚的转化率高达 99.2%，环己烷的产率高达 86.6%。此外，在 Ni/SiO 上，愈创木酚的转化率达到 100%，环己醇的产率达到 92.6%。更重要的是，Ni/SiO 和 Ni/ZSM-5（27）分别适用于具有不同取代基的芳香底物。
