五羰基铁对正辛硫醇中硫的脱除研究

由于能源化石类燃料中均包含不同含量的硫化物,随着人类对这些能源的不断利用,引发的环境污染等问题日趋严重。利用五羰基铁(Fe(CO)5)分解条件温和可控,产物无杂质,分解后的Fe0可以与硫原子原位键合等特点。文章尝试采用Fe(CO)5作为脱硫剂在温和条件下进行脱除正辛硫醇的研究。实验结果表明:随着压强(101~5 067 kPa)、Fe(CO)5加入量(50~250μL)、时间(1~6 h)和温度(0~180℃)的不同,Fe(CO)5脱硫效率具有明显差异,在此基础上得到最佳脱硫条件及最高脱除效率:常压、Fe(CO)5加入量200μL(1.4 mmol)、t=2h和T=140℃时,达到最高硫容3 450 mg/L。分别采用IR、XPS手段对脱硫反应机理进行了探索。IR结果表明:在1 084 cm-1处为硫氧峰,在797 cm-1归属为铁氧峰。XPS结果表明:167.8 eV处可能为S4+,711.6 eV处可能为Fe3+。因此,正辛硫醇脱除的可能机理为巯基断裂,并在空气中与氧结合,最终形成S4+,而Fe(CO)5的Fe经过脱硫之后,在空气中不稳定,最终被氧化成Fe3+。

Removing Sulfur from 1-Octanethiol by Fe(CO)5

Decomposing of Fe(CO)5 is characterized by mildness,no impurities in the decomposing products and the lone-pair electron of sulfur that can be combined with Fe0.Thus an investigation was conducted to use Fe(CO)5 as a sorbent removing 1-Octanethiol in purpose to explore a new method of desulfurization for fossil fuels.Result of the investigation showed the optimum condition was pressure 1 atm,dosage of Fe(CO)5 200 μL,time 2 h,and temperature 140 ℃.The desulfurization was characterized by FTIR and XPS by which it could be presumed that mechanism of sulfur-removing was due to the bond-breaking of sulfur-hydrogen of 1-Octanethiol,which was followed by combination of S with oxygen to form S4+,and Fe of Fe(CO)5 which was unstable in the air was oxidized into Fe3+ finally.