噻吩水热裂解平衡计算及反应过程分析

Equilibrium calculation of thiophene hyodropyrolysis and reaction mechanism analysis

采用乘子法 ,结合Gibbs自由能最小的概念 ,计算注蒸汽热采地层条件下 ,噻吩水热裂解反应体系的平衡组成 .根据实验数据和计算结果分析反应过程 ,认为噻吩水热裂解过程中发生了水解、热解、加氢脱硫、加氢饱和及水煤气转换等反应 .平衡计算结果表明 ,当水 /噻吩摩尔进料比小于 4时 ,提高进料比有利于脱硫 ,并生成更多气体 ;提高反应温度、降低反应压力有利于提高气体产量 ,但不利于脱硫 .当水 /噻吩摩尔进料比大于 4时 ,噻吩平衡转化率达 10 0 % ,温度、压力、进料比对平衡组成的影响很小 .

The equilibrium composition of thiophene hydropyrolysis during steam stimulation was calculated by using the method of multiplier and the concept of minimum Gibbs free energy. The reaction mechanism was analyzed by using laboratory data and equilibrium calculation. The results indicated that hydrolyzation, pyrolysis, hydrodesulfurization, hydrogenation and water gas shift were the main reactions of thiophene hydropyrolysis. When the molar ratio of water to thiophene was less than 4, a higher molar ratio favored both desulfurization and higher gas yield. Only higher gas yield was achieved if the reaction temperature was higher and the pressure was lower. Complete conversion of thiophene could be achieved when the molar ratio of water to thiophene was greater than 4. Temperature, pressure and feed ratio had little effect on the equilibrium composition under this condition.