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原油饱和烃与硫酸钙和元素硫的程序升温模拟实验中,通过分析反应过程中有机气态烃(C1～C5)和无机气体H2,H2S,CO2等组分的产率变化及其演化特征,剖析了模拟实验中的反应机理和反应机制.硫酸钙-饱和烃系列中,H2S的生成量很少,属反应程度较低的TSR反应,整个体系以烃类自身热裂解为主.元素硫-饱和烃系列中,由于元素硫受热生成硫自由基而具有显著的催化作用,加速了烃类烷基基团C—H键的裂解,C—H键的裂解碳造成了CO2产率的提高,C—H键的裂解氢生成H2的同时,与硫自由基结合生成大量的H2S,整个体系属硫自由基的催化反应.元素硫-饱和烃系列中,由于硫在低温阶段对C6+烃类裂解的促进作用和高温阶段对气态烃的消耗作用,造成元素硫和硫酸钙两个系列烃类气体产率曲线出现交叉现象.
Through the simulation experiment of temperature rising of saturated hydrocarbon, calcium sulfate and elemental sulfur, the yield changes and evolution characteristics of organic gaseous hydrocarbons (C1-C5) and inorganic gases such as H2, H2S and CO2 during the reaction were analyzed. The reaction mechanism and reaction mechanism in the simulation experiment are as follows: In the calcium sulphate-saturated hydrocarbon series, the formation of H2S is very little, which is a less reactive TSR reaction and the whole system is dominated by the self-pyrolysis of hydrocarbons. Hydrocarbon series, due to the elemental sulfur generated by the sulfur free radicals and has a significant catalytic effect, accelerating the hydrocarbon alkyl group C-H bond cleavage, C-H bond cleavage of carbon dioxide yield increased, C H bond cleavage of hydrogen to generate H2 at the same time, combined with the sulfur free radicals to generate a large number of H2S, the whole system is a sulfur radical catalytic reaction. Elemental sulfur - saturated hydrocarbon series, the sulfur in the low temperature of C6 + hydrocarbons cracking The accelerating effect and the depletion of gaseous hydrocarbons during the high temperature phase lead to the crossover of the yield curves of the two series of hydrocarbon gases of elemental sulfur and calcium sulfate.