页岩油加氢脱氮集总动力学模型研究

针对页岩油加氢改质过程中氮化物脱除特点,将原料油中氮化物依据脱除活性划分为2、3、4或5个集总,建立4种相应的加氢脱氮集总动力学模型。模型考虑了反应压力、液时空速、氢/油体积比及氮化物自阻碍因素对不同集总加氢脱氮反应的影响。以60个实验数据点为基础,求解得到动力学模型参数。对比4种动力学模型拟合效果和外推效果,并选用最佳模型预测原料油加氢脱氮最佳工艺条件。结果表明,4种模型相关系数均大于09983,均方差均小于19,较为合理。五集总模型拟合效果最好,拟合相对误差小于5%,可以较好地描述页岩油中氮化物脱除反应。五集总模型预测的龙口页岩油加氢脱氮最佳工艺条件为反应温度69315 K、反应压力9 MPa、液时空速05 h-1,与工艺条件考察实验结果一致。

Lumping Kinetic Models of Shale Oil Hydrodenitrogenation

Four kinds of hydrodenitrogenation (HDN) lumping kinetic models for shale oil were proposed and compared with each other in the prediction capability for nitrogen contents of hydrotreated oil samples. The nitrogen compounds in the feedstock were lumped into two, three, four or five portions, respectively, in terms of the different reactivity and reaction rate of HDN reaction. The influences of hydrogen pressure, LHSV, hydrogen oil ratio and the nitrogen compounds inhibition effects on HDN were considered in the models. The kinetic parameters were obtained on the basis of data from sixty experiments. The optimal model was selected after comparing the fitting and prediction effects of the models, and applied to predict the most reasonable conditions for shale oil hydrodenitrogenation. The results showed that all the five kinetic models were reasonable with the correlation coefficients greater than 0.9983 and mean square errors less than 1.9. Among the five models, the five lump kinetic model had the best fitting effect, and could better describe the HDN reactions in shale oil. The relative errors between predicted and experimental data were less than 5%. The optimal conditions for Longkou shale oil HDN predicted by the five-lump model were the reaction temperature of 69315 K, reaction pressure of 9 MPa, LHSV of 0.5 h^-1, under which the predicted data were similar to the experimental results.