柴油加氢NiMo催化剂新鲜剂与工业旧剂反应规律实验研究  

Experimental Study on the Reaction Pattern Between Fresh and Industrial Deactivation NiMo Catalysts for Diesel Hydrogenation

作　　者：章晓岩 丁石 胡志海 聂红 ZHANG Xiaoyan;DING Shi;HU Zhihai;NIE Hong(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）》2023年第4期827-834,共8页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：中国石油化工股份有限公司项目(121025)资助。

摘　　要：以混合柴油为原料,在中型固定床加氢实验装置上,对柴油加氢NiMo催化剂新鲜剂与工业旧剂2种催化剂在不同温度和空速条件下的反应规律进行研究。结果表明,相比新鲜剂,工业旧剂发生了明显的失活,催化剂孔结构发生明显变化,不同加氢反应发生的活性损失并不一致。工业旧剂可以通过提高反应温度、降低空速的方法提高脱氮率和脱硫率,但无法脱除难反应硫化物。对于多环芳烃饱和反应,随反应温度升高存在热力学平衡限制,产品中多环芳烃含量存在最小值;空速对新鲜剂影响大于工业旧剂,降低空速有利于芳烃饱和。根据实验数据建立了催化剂失活动力学模型,研究了失活催化剂加氢脱硫反应和多环芳烃饱和反应指前因子变化规律,通过动力学模型能够预测失活催化剂各个加氢反应活性损失程度,以及不同空速条件下催化剂能够生产国Ⅵ柴油的指前因子比值临界值。通过动力学模型计算发现,催化剂失活前后反应活化能变化不大,指前因子变化明显,当加氢脱硫反应指前因子比值为0.37、多环芳烃饱和反应指前因子比值为0.12时,可以在液时空速为0.67 h^(-1)时生产出满足国Ⅵ标准的柴油。Using the mixed diesel fuel as raw materials,the reaction patterns between the fresh agent and industrial deactivation agent of NiMo catalysts for diesel hydrogenation were investigated at different temperatures and air velocities on a medium-sized fixed bed hydrogenation experimental device.The results show that the industrial deactivation catalysts have underwent significant deactivation as compared with the fresh catalysts,and the catalyst pore structure has suffered from significant degradation and the loss of activity is not consistent in different hydrogenation reactions.The industrial deactivation catalysts can improve the denitrification rate and desulfurization rate by increasing the reaction temperature and lowering the air velocities,but refractory sulfides are hard to remove.For polycyclic aromatic hydrocarbon(PAH)saturation reactions,there is a thermodynamic equilibrium limit with the increasing of reaction temperature,and there is a minimum value for PAH content of the product;the air velocity has a greater effect on the fresh agent than the industrial deactivation agent,and lowering the airspeed is beneficial to aromatic saturation.A deactivation kinetic model of catalyst was developed based on experimental data to investigate the changes in pre-exponential factors for the hydrodesulfurization and PAH saturation reactions of deactivated catalysts.The kinetic model is able to predict the degree of activity loss in each hydrogenation reaction of the deactivated catalysts and the critical values of the pre-exponential factor ratios for the catalysts to produce China nationⅥstandard diesel at different liquid hourly space velocities(LHSV).The calculation based on the kinetic model reveals that the activation energy of the reaction before and after deactivation changes little,but the pre-exponential factor shows an obvious change.When the pre-exponential factor ratio of the hydrodesulfurization reaction and PAH saturation reaction is 0.37 and 0.12,respectively,diesel fuel meeting the China nationalⅥ

关 键 词：新鲜催化剂 工业旧催化剂 失活 动力学 

分 类 号：TE624[石油与天然气工程—油气加工工程]