柴油加氢脱氮集总动力学模型及应用  

Lumped Kinetic Model and Application of Diesel Hydrodenitrogenation

作　　者：黄镇 鞠雪艳 丁石 聂红 习远兵 HUANG Zhen;JU Xueyan;DING Shi;NIE Hong;XI Yuanbing(SINOPEC Research Institute of Petroleum Processing Co.,Ltd.,Beijing 100083,China)

机构地区：[1]中石化石油化工科学研究院有限公司,北京100083

出　　处：《石油学报（石油加工）》2024年第1期175-182,共8页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：中国石油化工股份有限公司合同项目(120051-1)基金资助。

摘　　要：采用气相色谱-质谱(GC-MS)对柴油加氢过程中含氮化合物的类型进行识别,结合含氮化合物在氮化学发光检测器(NCD)上的保留及响应特性,得到不同工艺条件下含氮化合物的类型分布。基于咔唑侧链甲基数的不同,建立了包含反应温度、反应压力、液时空速、氢/油体积比以及杂质含量(硫化氢、碱性氮化物和非碱性氮化物)等影响因素的五集总Langmuir-Hinshelwood加氢脱氮(HDN)动力学模型;模型采用Levenberg-Marquardt方法求解,验证结果表明拟合值与实验值相吻合。动力学模型可用于HDN过程工艺条件的优化,结果表明,当反应温度为350℃、反应压力为6.4 MPa和氢/油体积比为300条件下,氮化物的脱除效果最优。The types of nitrogen compounds in diesel hydrogenation process were identified by gas chromatography-mass spectrometry(GC-MS).Further,based on the retention and response characteristics of nitrogen compounds on nitrogen chemiluminescence detector(NCD),the type distribution of nitrogen compounds under different process conditions was obtained.Considering the difference of methyl number in carbazole side chain,the five-lumped Langmuir-Hinshelwood hydrodenitrogenation(HDN)kinetic model was established involving the influencing factors such as reaction temperature,reaction pressure,liquid hourly space velocity,the volume ratio of hydrogen to oil and the content of impurities(hydrogen sulfide,basic and non-basic nitrides).The model was solved by the Levenberg-Marquardt method,and the verification results show that the fitted values agree well with the experimental data.On the basis,the model can be effectively used to optimize the HDN process conditions,and the calculated results indicate that the removal effect of nitrogen compounds is the best at the reaction temperature of 350℃,reaction pressure of 6.4 MPa and V(H_(2))/V(Oil)of 300.

关 键 词：NiMo催化剂 加氢脱氮 动力学模型 参数估计 预测 

分 类 号：TQ015.9[化学工程]