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基于黄金管模拟实验对原油裂解的动力学及控制因素进行了研究。通过气态烃的定量分析,发现原油的持续裂解使得总裂解气体积及CH4产量不断增加,而C2-5的产量则先增加后减少。动力学计算可得,HD11井原油裂解生气总反应的平均活化能为59.8 kcal/mol(250.0 kJ/mol),频率因子A为2.13×1013s-1。残留原油组分的色质分析结果表明,不同族组分的相对稳定性存在差异,且原油中的大分子更容易发生裂解。同时,不同介质条件下的对比实验结果及前人的研究,都证实了压力、水及粘土矿物等因素很可能影响甚至控制原油的裂解。尽管作用机制不同,高压和水的存在都能抑制裂解过程中的自由基链反应,从而起到提高原油稳定性的效果。而粘土矿物,尤其是蒙脱石或伊/蒙混层矿物,则会通过酸催化作用加速原油或烃类的裂解,且裂解气产率与矿物表面的Brnsted酸位强度成正相关。
The kinetics and control factors of crude oil cracking were studied based on gold tube simulation experiments. Through the quantitative analysis of gaseous hydrocarbons, it was found that the sustained cracking of crude oil led to the increase of total pyrolysis gas volume and CH4 production, while the yield of C2-5 firstly increased and then decreased. The kinetic calculation shows that the average activation energy of the total reaction of crude oil cracking HD11 is 59.8 kcal / mol (250.0 kJ / mol) and the frequency factor A is 2.13 × 1013s-1. The chromatographic analysis of residual crude oil shows that there is a difference in the relative stability of different components and that the larger molecules in crude oil are more susceptible to cleavage. At the same time, the comparative experimental results under different media conditions and previous studies confirm that factors such as pressure, water and clay minerals are likely to affect and even control the cracking of crude oil. Despite the different mechanism of action, the existence of high pressure and water can inhibit the free radical chain reaction in the pyrolysis process, thereby improving the stability of the crude oil. Clay minerals, especially montmorillonite or Iraqi / metamorphic minerals, accelerate the cracking of crude oil or hydrocarbons through acid catalysis, and the yield of cracked gas is positively related to Brnsted acid sites on mineral surfaces.