馏分油浆态床加氢处理研究：ⅡFCC柴油加氢工艺条件及动力学研究

A study on process for slurry-bed hydrotreating of distillate oil:Ⅱ Processing conditions and kinetics analysis of FCC diesel oil

对FCC柴油在浆态床柴油加氢催化剂SP25上的加氢工艺条件进行了优化,并考察了加氢脱硫(HDS)和加氢脱氮(HDN)动力学。结果表明,提高反应温度、提高反应压力、增加催化剂的加入量、延长反应时间都能提高催化剂的加氢精制活性,最佳的FCC柴油浆态床加氢工艺条件为,温度350℃、压力6MPa、催化剂加入量6%、反应时间2h。催化剂循环使用性能的考察结果表明,SP25催化剂具有良好的活性稳定性。动力学研究结果表明,FCC柴油的加氢脱硫反应过程可以分为两个阶段。第一阶段为较易脱除的苯并噻吩类(BTs)硫化物的加氢脱硫反应,反应活化能为70.00kJ/mol;第二阶段为较难脱除的二苯并噻吩类(DBTs)硫化物的加氢脱硫反应,反应活化能为85.65kJ/mol。FCC柴油HDN反应的活化能为79.91kJ/mol。烷基取代的二苯并噻吩类硫化物(特别是DMDBTs)是加氢精制反应中最难脱除的含杂原子(S或N)烃类化合物。

Slurry-bed hydrogenation processing conditions of FCC diesel oil were optimized, and hydrodesulfurization （HDS） and hydrodenitrogenation （HDN） kinetics were also studied over slurry-bed hydrogenation catalyst （SP25）. The results indicated that the catalyst activity increased with increase of reaction temperature （t）, pressure （p）, catalyst additional weight （ w lyst ） and reaction time （ t ）. The optimal process conditions were t = 350 ℃, p = 6 MPa, WcatatLyst = 6% , t = 2 h. The results of catalyst recycling performance suggested that catalyst SP25 possessed good activity stability. Kinetic data showed that the FCC diesel oil HDS reaction could take place in two reaction stages. The first stage is HDS of benzothiophenes （ BTs）, which are easier to be hydrodesulfurized among sulfur-containing compounds in FCC diesel oil. The reaction activation energy is 70.00 k J/tool. The second is I-IDS of dibenzothiophenes （ DBTs）, which are more difficult to be hydrodesulfurized. The reaction activation energy is 85.65 kJ/mol. The reaction activation energy for diesel I-IDN reaction is 79.91 kJ/mol. Alkyl-DBTs, especially DMDBTs were the the most difficult to be removed heteroatom-containing（ S and/or N） hydrocarbon compounds in hydrotreating reaction.