过氧化氢-甲酸氧化模拟柴油脱硫试验及其动力学分析

以正辛烷-二苯并噻吩模拟柴油,进行过氧化氢-甲酸氧化脱硫试验和动力学研究。结果表明,过氧化氢-甲酸体系能够有效氧化模拟柴油中的二苯并噻吩,生成二苯并噻吩砜。影响脱硫率的因素顺序为:甲酸用量温度过氧化氢用量。优化条件为:V(模拟柴油)∶V(H2O2)∶V(HCOOH)=100∶1∶10,40℃下反应1 h,硫的质量分数可由1.14×10-3降至1.14×10-5,脱硫率为99.01%。该条件下计算动力学参数得反应级数1.055 4,速率常数5.15×10-2(μg/g)1-n.min-1。

Oxidative desulfurization of a model diesel fuel using an H2O2-formic acid system and its kinetic analysis

The oxidative desulfurization of a model diesel fuel (which was prepared by mixing n-octane and dibenzothiophene (DBT)) has been carried out using H2O2-HCOOH. Formic acid showed better catalytic ability than other acids, with DBT in the model diesel fuel being converted into a polar substance that was shown to be dibenzothiophene sulfone. The sensitivity of desulfurization efficiency to the experimental parameters decreased in the order HCOOH content>temperature>H2O2 content, according to orthogonal tests. Furthermore, when reacting for 1h at 40℃ and atmospheric pressure, with the addition of 1% volume fraction of H2O2 and 10% HCOOH, the mass fraction of sulfur was reduced from 1.14 × 10-3 to 1.14 × 10-5 without any the need for any extraction, and the desulfurization efficiency reached 99.01%. A kinetic study under these conditions showed that the reaction or der was 1.0554, and the rate constant was 5.15 × 10-2(μg/g)1-n·min-1.