桦甸页岩油柴油馏分加氢精制生产清洁燃料油的研究

Hydrotreating of the diesel distillate from Huadian shale oil for production of clean fuel

柴油馏分（200℃-360℃）在桦甸页岩油中约占41%。其中,硫、氮及不饱和烃含量较高,含硫化合物以苯并噻吩类及二苯并噻吩类化合物为主,而氮化物中的碱性氮化物和非碱性氮化物的含量相当。实验中分别以硫化态的CoMo/Al2O3及NiW/Al2O3为催化剂,利用固定床小型加氢反应装置,考察了不同工艺条件对桦甸页岩油柴油馏分加氢脱硫及加氢脱氮效果的影响。结果表明,反应温度升高,增大反应压力,降低体积空速,对脱硫、脱氮都是有利的,特别是对加氢脱氮影响最为明显,而氢油体积比的影响相对较小。两种催化剂活性比较发现,对于该页岩馏分油而言,两种催化剂的加氢脱硫效果相差不大,而NiW/Al2O3的加氢脱氮效果却明显好于CoMo/Al2O3。在选择的工艺条件下,对桦甸页岩油柴油馏分进行加氢精制得到的产品油中杂原子和不饱和烃含量低,密度小,芳香烃含量少,可作为优质清洁柴油直接使用。

The diesel distillate（200 ℃~360 ℃）accounting for about 41% in Huadian shale oil has higher sulphur,nitrogen and alkene contents.The main sulphur-containing compounds in the diesel distillate are BTs（benzylthiophene） and DBTs（di benzylthiophene）,and the content of basic nitrogen compound in the distillate approaches to that of nonbasic nitrogen compound.In order to produce a clean fuel,the catalytic hydrotreating of diesel fraction from Huadian shale oil was investigated preliminarily in a fixed bed reactor using two kind of commercial catalysts including CoMo/Al2O3 and NiW/Al2O3 at different temperatures,hydrogen pressures,LHSVs（Liquid hourly space velocity） and the ratios of hydrogen/feedstock.The results show that increasing temperature,hydrogen pressure and residence time（reciprocal LHSV） can promote the removal of sulfur and nitrogen,while the hydrogen/feedstock ratio has little influence.The catalyst NiW is more active for hydrodenitrogenation（HDN） than CoMo.Under relative mild conditions,the diesel can be produced from Huadian shale oil distillate with low contents of sulfur,nitrogen and alkene,and lower density and higher cetane number,which can be used as a high quality fuel.