College of Nanotechnology, King Mongkut's Institute of Technology Ladkrabang, Chalongkrung Rd., Ladkrabang, Bangkok 10520, Thailand.
Energy Catalyst Technology Group, Energy Process Research Institute (EPRI), National Institute of Advanced Industrial Science and Technology (AIST), 16-1 Onogawa, Tsukuba, Ibaraki 305-8559, Japan.
Int J Mol Sci. 2021 Jan 27;22(3):1256. doi: 10.3390/ijms22031256.
To improve the oxidative stability of biodiesel fuel (BDF), the polyunsaturated fatty acid methyl esters (poly-FAME) presented in commercial palm oil-derived biodiesel fuel (palm-BDF) were selectively hydrogenated to monounsaturated fatty acid methyl esters (mono-FAME) under a mild condition (80 °C, 0.5 MPa) using activated carbon (AC)-supported Pd catalysts with a Pd loading of 1 wt.%. The partially hydrotreated palm-BDF (denoted as H-FAME) which has low poly-FAME components is a new type of BDF with enhanced quality for use in high blends. In this study, we reported that the chemical states and particle sizes of Pd in the prepared Pd/AC catalysts were significantly influenced by the Pd precursors, Pd(NO) and Pd(NH)Cl, and thus varied their hydrogenation activity and product selectivity. The 1%Pd/AC (nit) catalyst, prepared using Pd(NO), presented high performance for selective hydrogenation of poly-FAME into mono-FAME with high oxidation stability, owning to its large Pd particles (8.4 nm). Conversely, the 1%Pd/AC (amc) catalyst, prepared using Pd(NH)Cl, contained small Pd particles (2.7 nm) with a little Cl residues, which could be completely removed by washing with an aqueous solution of 0.1 M NHOH. The small Pd particles gave increased selectivity toward unwanted-FAME components, particularly the saturated fatty acid methyl esters during the hydrogenation of poly-FAME. This selectivity is unprofitable for improving the biodiesel quality.
为了提高生物柴油燃料(BDF)的氧化稳定性,在温和条件(80°C,0.5 MPa)下,使用负载量为 1wt%的活性炭(AC)负载钯催化剂,将商业棕榈油衍生生物柴油燃料(棕榈-BDF)中存在的多不饱和脂肪酸甲酯(多-FAME)选择性加氢为单不饱和脂肪酸甲酯(单-FAME)。部分加氢处理的棕榈-BDF(表示为 H-FAME)具有低多-FAME 成分,是一种新型 BDF,质量得到提高,可用于高掺混比。在这项研究中,我们报告称,Pd 前驱体 Pd(NO)和 Pd(NH)Cl 显著影响了所制备的 Pd/AC 催化剂中 Pd 的化学状态和颗粒大小,从而改变了它们的加氢活性和产物选择性。使用 Pd(NO)制备的 1%Pd/AC(nit)催化剂,由于其大的 Pd 颗粒(8.4nm),对多-FAME 选择性加氢为单-FAME 表现出高的氧化稳定性和高的性能。相反,使用 Pd(NH)Cl 制备的 1%Pd/AC(amc)催化剂,含有小的 Pd 颗粒(2.7nm)和少量的 Cl 残留,这些残留可以通过用 0.1M NH₃·H₂O 水溶液洗涤完全去除。小的 Pd 颗粒在多-FAME 的加氢过程中,增加了对不需要的-FAME 成分,特别是饱和脂肪酸甲酯的选择性。这种选择性不利于提高生物柴油的质量。