高硫石油焦的脱硫研究

采用湿化学氧化和高温煅烧相结合的方法对含硫量6.28%(w)的石油焦进行二段脱硫处理,并利用FTIR、SEM和XRD技术对脱硫机理进行了探讨。实验结果表明:氧化工段的优化条件为硝酸与30%(w)双氧水的体积比1∶2、氧化时间10 h、氧化温度80℃、液固比35 m L/g、石油焦粒径106μm以下,优化条件下的氧化脱硫率为26.91%;煅烧工段的优化条件为1 280℃下煅烧6 h,优化条件下的煅烧脱硫率为79.43%,总脱硫率为83.95%。表征结果显示:经处理后石油焦中的黄铁矿类无机硫以及硫醇类和大部分噻吩类有机硫得到有效脱除,剩余噻吩硫转变为更稳定的形式;处理后的石油焦微观形貌轮廓变得清晰和圆润;处理前后石油焦的石墨雏晶结构基本未发生变化。

Desulphurization of high-sulfur petroleum coke

The petroleum coke with 6.28% of sulfur content（w）was treated by a two-stage desulphurization of wet chemical oxidation combined with high temperature calcination,and the desulfurization mechanism was discussed by using FTIR,SEM and XRD technology. The experimental results show that：The desulphurization rate by chemical oxidation is 26.91% under the optimized conditions of volume ratio of nitric acid to 30%（w）H₂O₂ solution 1∶2,oxidation time 10 h,oxidation temperature 80 ℃,the liquid-solid ratio 35 mL/g and petroleum coke size below 106 μm;The desulfurization rate by calcination can reach 79.43% under the optimized conditions of calcination temperature 1 280 ℃ and calcination time 6 h,and the total desulphurization rate is 83.95%. The characterization results show that：After the two-stage treatment,inorganic sulfur in pyrite and organic sulfur in thiol and most thiophene are removed effectively,and the rest of thiophenic sulfur turns into a more stable form;The microstructure and profile of the treated petroleum coke become clear and round,while the graphite crystallite structure of it has little change.