中温热解焦油重馏分悬浮床加氢裂化的研究
Study on suspension bed hydrocracking of medium temperature pyrolytic heavy tar fraction
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摘要: 以中温热解煤焦油为原料, 对其性质进行了分析, 其中, >350 ℃重质馏分中胶质含量30.88%, 沥青质含量37.27%, 四氢呋喃不溶物3.36%, 属于常规固定床加氢裂化难以直接处理的馏分。合成了一种Mo系超分散催化剂, 采用FT-IR、XPS、XRD、SEM和TEM等对催化剂进行了表征, 催化剂中含有Mo=O和Mo-S特征结构, 活性金属的硫化率为84.34%, 在体系中具有优良的分散性, 在反应体系内原位分解为超分散MoS2颗粒;在0.25 t/d连续装置上进行了热解重油悬浮床加氢裂化实验研究, 考察了反应条件对产物分布情况和结焦率的影响, 得出适宜的反应条件为19 MPa, 440 ℃, 催化剂的添加量为300 mg/kg;此条件下石脑油收率24.47%, 柴油馏分收率49.71%, 结焦率1.32%。Abstract: The medium temperature pyrolytic coal tar was used as raw material and was analyzed, in which the fraction with boiling point > 350 ℃ that contains the resin of 30.88%, the asphaltene of 37.27% and the tetrahydrofuran insolubles of 3.36% is difficult to hydrocrack directly by conventional fixed bed. A Mo-based ultra-dispersed catalyst was synthesized, and characterized by FT-IR, XPS, XRD, SEM and TEM, etc. The catalyst contains Mo=O and Mo-S characteristic structure and has an excellent dispersibility in the reaction system, and the vulcanization ratio of molybdenum reaches 84.34%. The catalyst can be decomposed into hyper dispersive MoS2 particle in the reaction system. The suspension bed hydrocracking experiments were carried out in a 0.25 t/d continuous unit with heavy fraction of tar. Moreover, the effects of reaction conditions on product distribution and coking rate were investigated. The optimum reaction conditions were 19 MPa, 440 ℃ and 300 mg/kg of catalyst addition. Under these conditions, the naphtha yield is 24.47%, the diesel fraction yield is 49.71%, and the coking rate is 1.32%.