Ti-MCM-41/H_2O_2·HCOOH催化氧化模拟汽油中噻吩的选择氧化及动力学

SELECTIVE OXIDATION AND KINETICS OF Ti-MCM-41/H_2O_2·HCOOH SYSTEM FOR THIOPHENE IN SIMULATED GASOLINE

以正辛烷为溶剂、噻吩(THP)为模型硫化合物组成模拟轻质油品,以自合成的中孔分子筛Ti-MCM-41为催化剂,H2O2和HCOOH分别为氧化剂和助氧化剂,对其进行氧化抽提脱硫实验。采用正交实验得到较佳反应条件,即H2O2添加量为体积分数1%、反应时间40min、反应温度50℃。在此条件下,噻吩脱除率为95.6%,油收率为98.7%。进一步考察了Ti-MCM-41分子筛不同用量和重复利用次数对反应脱硫率和油品收率的影响。动力学研究表明,以Ti-MCM-41/H2O2.HCOOH为催化氧化体系,模拟轻质油中噻吩的脱除反应为表观一级反应,反应活化能Ea为40.18kJ/mol。

A simulated oil consisting of thiophene as model sulfur compounds and as solvent was employed for the oxidative extraction desulfurization in catalytic oxidative system of Ti-MCM-41/ H2O2@HCOOH. By using orthogonal design, the optimal reaction time, temperature, amount ofH2O2 and all significant factors affecting the desulfurization of simulated oil containing thiophene were obtained, including the H2 02 addition volume fraction of 1%, the reaction temperature of 50 ℃ and the time of 40 min, under which the removal ratio of thiophene was 95.6% and gasoline yield was 98.7%. The influences of dosage and reuse times of Ti-MCM-41 on removal ratio of thiophene were also investigated. From the kinetics study, it indicated that the reaction was a pseudo first- order reaction, and the activation energy E, is 40.18 kJ/mol.