摘要
It is urgent to develop a new deep desulfurization process of fuels as the environmental pollution increases seriously. In this work, a series of Lewis acidic ionic liquids （ILs） [C43MPy]Cl/nZnCl2 （n=1, 1.5, 2, 3） were synthesized and used in extraction and catalytic oxidative desulfurization （ECOD） of the fuels. The effects of the Lewis acidity of ILs, the molar ratio of H2O2/sulfur, temperatures, and different substrates including dibenzothiophene （DBT）, benzothiophene （BT） and thiophene （TS）, on sulfur removal were investigated. The results indicated that [C43MPy]Cl/3ZnCl2 presented near 100% DBT removal of model oil under conditions of 323 K, H2O2/DBT molar ratio 6：1. Kinetics for the removal of DBT, BT and TS by the [C43MPy]Cl/3ZnCl2-H2O2 system at 323 K is first-order with the apparent rate constants of 1.1348, 0.2226 and 0.0609 h-1, and the calculated apparent activation energies for DBT, BT and TS were 61.13, 60.66, and 68.14 kJ/mol from 298 to 308 K, re- spectively. After six cycles of the regenerated [C43MPy]Cl/3ZnCl2, the sulfur removal had a slight decrease. [C43MPy]Cl/ 3ZnCl2 showed a good desulfurization performance under optimal conditions.
当环境污染严重增加，开发燃料的一个新深 desulfurization 过程是迫切的。在这个工作，一系列路易斯酸的离子的液体(IL )[C <sub>4</sub><sup>3</sup > MPy ] Cl/nZnCl <sub>2</sub>(n=1， 1.5， 2， 3 ) 在抽取和燃料的催化氧化 desulfurization (ECOD ) 被综合并且使用。IL 的吊楔酸味的效果， H <sub>2</sub 的臼齿的比率 > 包括 dibenzothiophene (DBT ) 的 O <sub>2</sub>/sulfur, 温度，和不同底层， benzothiophene (BT ) 和 thiophene (TS ) ，在硫上，移动被调查。结果显示了那[C <sub>4</sub><sup>3</sup > MPy ]Cl/<sub>3</sub > ZnCl <sub>2</sub> 在 323 K 的条件下面介绍了模型油的近的 100% DBT 移动， H <sub>2</sub > O <sub>2</sub>/DBT 臼齿的比率 6:1。为 DBT ， BT 和 TS 由的移动的动力学[ C <sub>4</sub> <sup>3</sup > MPy ]Cl/ <sub>3</sub > ZnCl <sub>2</sub>-H<sub>2</sub >在 323 K 的 O <sub>2</sub>系统为 DBT 与 1.1348 ， 0.2226 和 0.0609 h <sup>-1</sup>,和计算明显的激活精力的明显的率常数是一阶的， BT 和 TS 分别地是从 298～308 K 的 61.13 ， 60.66 ，和 68.14 kJ/mol 。在六个周期以后再生[CC <sub>4</sub><sup>3</sup > MPy ]Cl/<sub>3</sub > 硫移动有的 ZnCl <sub>2</sub>, 细微减少。[CC <sub>4</sub><sup>3</sup > MPy ]Cl/<sub>3</sub > ZnCl <sub>2</sub> 在最佳的条件下面显示出好 desulfurization 表演。
基金
supported by the National Natural Science Foundation of China (21576262, 21206169)
International S&T Cooperation Program of China (2014DFA61670)
the “Recruitment of Outstanding Technologist” of Chinese Academy of Sciences
