元素硫促进原油烃类热裂解及其对TSR作用启动机制的影响

The initial H₂S in the quartz tube closed reaction system provided by S was utilized, and the influence of S on the thermal cracking process of crude oil hydrocarbons and the initiation mechanism of thermochemical sulfate reduction (TSR) was studied through a comparative study of the thermal simulation experiments of crude oil with calcium sulfate or magnesium sulfate under water-bearing conditions. The results show that under the water-bearing experimental conditions above 336 °C, hydrocarbons can reduce all S into H₂S in a short time. H₂S has an obvious promoting effect on the thermal cracking of crude oil into gas, significantly increasing the yields of hydrocarbon gases and CO₂, and at the same time increasing the dryness coefficient of the gas. The H₂S generated by the reduction of S easily reacts with hydrocarbons to form unstable sulfur-containing compounds, and this organosulfur intermediate plays an important role in the process of S-catalyzed thermal cracking of hydrocarbons. Combining the δ³⁴S of H₂S generated in the experiment and the H₂S/S₀ of the generated gas, it was found that magnesium sulfate is more likely to initiate the TSR reaction than the sparingly soluble calcium sulfate.

利用S提供石英管封闭反应体系中的初始H_2S,通过原油与硫酸钙或硫酸镁在含水条件下的热模拟实验对比研究S对原油烃类热裂解过程及热化学硫酸盐还原(TSR)作用启动机制的影响。结果表明,在大于336 ℃含水实验条件下,烃类能够在短时间内将S全部还原成H_2S。H_2S对原油热裂解成气有明显促进作用,使烃类气体和CO_2的产率显著增加,同时提高气体的干燥系数。S还原生成的H_2S易与烃类反应生成不稳定含硫化合物,该有机硫中间体在S催化烃类热裂解过程发挥重要作用。结合实验中生成H_2S的δ~(34)S和生成气体的H_2S/S0发现,硫酸镁比难溶的硫酸钙更易启动TSR反应。