利用供氢剂探讨石油渣油的热转化机理(英文)

INVESTIGATION ON THERMAL TREATMENT MECHANISM OF PETROLEUM RESIDUE USING H-DONOR AS A PROBE

以孤岛渣油和辽河渣油为原料、以供氢剂 9,10 二氢蒽为化学探针 ,在反应温度 36 0℃～ 430℃和体系初压为室温时 4 0MPa氮气氛的热反应条件下 ,在微型高压釜内对渣油热转化机理随反应温度的变化进行了初步探讨。化学探针在渣油中的供氢反应遵循一级反应动力学模型 ;其中孤岛渣油反应体系中的供氢反应速率常数较辽河渣油中的大 ,并且其间的差别随温度升高而增大。虽然两种渣油反应体系中的氢转移反应积分活化能极为接近 ,但是微分活化能随温度升高而显著降低 ;这表明氢转移机理从较低温度时以分子间的反应为主转变为在较高温度时以自由基参与的反应为主。

The shift in thermal treatment mechanism of petroleum residue was tentatively investigated using two typical Chinese residua from Gudao and Liaohe oilfields as feedstocks in the presence of a chemical probe (dihydroanthracene, a hydrogen donor) over a temperatures range between 360℃～430℃ and under an initial pressure of 4?MPa of nitrogen gas at room temperature. The hydrogen-donating reaction of the chemical probe in residue kinetically followed a first-order reaction model. The kinetic rate constant of Gudao residue was greater than that of Liaohe residue, and the difference between them increased with temperature rise. Although integral activation energies of the hydrogen-transfer reaction in both residua were quite similar, both differential activation energies decreased with temperature rise, which suggested a shift in the hydrogen-transfer mechanism from a more molecular nature to a more free radical one as reaction temperature increased.