廢輪胎熱裂解油以快速混合輔助氧化脫硫系統資源化再利用之研究 ; The study of High-Speed Mixing assisted Oxidative Desulfurization Process on the Utilization of Pyrolysis Oil from Waste Tires

柴油中含有之長鏈碳有機化合物極適合作為燃料使用，但因含高濃度之有機硫成分，於燃燒過程容易產生SO2的排放，形成對環境的汙染及人體之危害。本研究利用超音波輔助氧化方式進行有機硫及柴油的脫硫試驗，針對化石燃油中具高含量之Benzothiophenes及Dibenzothiophenes家族進行研析，實驗選擇異多體酸為催化劑及不同之介面活性劑(四辛基磷鹽及四辛基銨鹽)進行試驗，並針對其不同之結合陰離子(溴及氟離子等)進行探討。實驗顯示：Benzothiophenes及Dibenzothiophenes家族均可在15分鐘之反應時間及80 oC的實驗溫度下，氧化為對應之? (Sulfone)，轉換效率達到99%。此外，使用柴油進行氧化脫硫測試可達100% 之去除率。最後，本研究亦建立此實驗合適之反應機制模型，並計算不同有機硫化物之氧化動力模式，以作為後續研究之依據。 ; Elevated concentration of sulfur in diesel fuel is one of the major contributors to air pollution. To limit the amount of sulfur in fuel, ultrasound-assisted oxidative desulfurization (UAOD) was studied using a model and actual diesel fuel over two types of phase transfer catalysis (PTC) catalysts namely ammonium and phosphonium salt. Specifically, the effect of the nature of the PTC catalyst on desulfurization efficiency was determined as well the recyclability of the catalyst. Surfactant-type phase transfer catalysts were found to display high catalytic activity with tetraoctylphosphonium fluoride (TOPF) being the most effective PTC catalyst among those examined. Treatment of model diesel fuel demonstrated 99 % conversion to polar sulfones, specifically benzothiophene sulfone (BTO) and dibenzothiophene sulfone (DBTO), were achieved at of the process with reaction temperature of 80 oC in less than 15 minutes of treatment. Using an actual diesel, the presence of the sulfur compounds was not detected after oxidation. In combination with adsorption, the desulfurization efficiency of 100 % was achieved at the end of the process. The influence of reaction temperature on the conversion of the sulfur compound and selectivity towards the polar sulfone was also studied. Finally, a suitable mechanism for PTC has been proposed and a kinetic model had been developed to be the fundamental of future experimental studies.